Evaporative emission control articles including activated carbon

ABSTRACT

The present disclosure relates to hydrocarbon emission control systems. More specifically, the present disclosure relates to substrates coated with hydrocarbon adsorptive coating compositions and evaporative emission control systems for controlling evaporative emissions of hydrocarbons from motor vehicle engines and fuel systems. The hydrocarbon adsorptive coating compositions include particulate carbon having a BET surface area of at least about 1300 m 2 /g, and at least one of (i) a butane affinity of greater than 60% at 5% butane; (ii) a butane affinity of greater than 35% at 0.5% butane; (iii) a micropore volume greater than about 0.2 mug and a mesopore volume greater than about 0.5 ml/g.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of International Application No.PCT/CN2019/095842, filed Jul. 12, 2019, and which claims priority toInternational Application No. PCT/CN2018/095773, filed Jul. 16, 2018,the contents of each of which are hereby incorporated by reference intheir entirety.

FIELD OF THE INVENTION

The present disclosure relates generally to hydrocarbon emission controlsystems. More particularly, the present disclosure relates to substratescoated with hydrocarbon adsorptive coating compositions, evaporativeemission control system components, and evaporative emission controlsystems for controlling evaporative emissions of hydrocarbons from motorvehicle engines and fuel systems.

BACKGROUND OF THE INVENTION

Evaporative loss of gasoline fuel from the fuel systems of motorvehicles powered by internal combustion engines is a major potentialcontributor to atmospheric air pollution by hydrocarbons. Evaporativeemissions are defined as emissions that do not originate from theexhaust system of the vehicle. The main contribution to the overallevaporative emissions of a vehicle is hydrocarbon fuel vaporsoriginating from the fuel system and the air intake system. Canistersystems that employ activated carbon to adsorb the fuel vapor emittedfrom the fuel systems are used to limit such evaporative emissions.Currently, all vehicles have a fuel vapor canister containing activatedcarbon pellets to control evaporative emissions. Activated carbon is thestandard adsorbent material used in all automotive evaporative emissioncontrol technologies, which typically make use of the activated carbonas an adsorbent material to temporarily adsorb the hydrocarbons.

The activated carbon is then periodically regenerated by purge air fromthe intake system, which desorbs the hydrocarbons and carries them intothe engine. Thus the activated carbon undergoes many thousands ofadsorption/desorption cycles over the lifetime of the vehicle. Duringeach adsorption cycle, a small amount of irreversible adsorption occurswhich is not regenerated. Over the lifetime of the vehicle, this smallamount of irreversible adsorption slowly increases, decreasing itsoverall effective adsorption capacity of the activated carbon. Thisphenomenon is referred to as heel or heel build.

Many fuel vapor canisters also contain an additional control device tocapture fuel vapors that escape from the carbon bed during the hot sideof diurnal temperature cycling. Current control devices for suchemissions contain exclusively carbon-containing honeycomb adsorbents forpressure drop reasons. In such systems, the adsorbed fuel vapor isperiodically removed from the activated carbon by purging the canistersystems with fresh ambient air, desorbing the fuel vapor from theactivated carbon and thereby regenerating the carbon for furtheradsorption of fuel vapor. Exemplary U.S. patents disclosingcanister-based evaporative loss control systems include U.S. Pat. Nos.4,877,001; 4,750,465; and 4,308,841.

Institution of strict regulations for permissible quantities ofhydrocarbon emissions have required progressively tighter control of thequantity of hydrocarbon emissions from motor vehicles, even duringperiods of disuse. During such periods (i.e., when parked), vehicle fuelsystems may be subject to warm environments, which result in increasedvapor pressure in the fuel tank and, consequently, the potential forevaporative loss of fuel to the atmosphere.

The afore-mentioned canister systems possess certain limitations inregard to capacity and performance. For example, purge air does notdesorb the entire fuel vapor adsorbed on the adsorbent volume, resultingin residual hydrocarbons (“heel”) that may be emitted to the atmosphere.The term “heel” as used herein refers to residual hydrocarbons generallypresent on an adsorbent material when the canister is in a purged or“clean” state and may result in a reduction of the adsorption capacityof the adsorbent. Bleed emissions, on the other hand, refer to emissionsthat escape from the adsorbent material. Bleed can occur, for example,when the equilibrium between adsorption and desorption favors desorptionsignificantly over adsorption. Such emissions can occur when a vehiclehas been subjected to diurnal temperature changes over a period ofseveral days, commonly called “diurnal breathing losses.” Certainregulations make it desirable for these diurnal breathing loss (DBL)emissions from the canister system to be maintained at very low levels.For example, as of Mar. 22, 2012, California Low Emission VehicleRegulation (LEV-III) requires canister 2-day DBL emissions for 2001 andsubsequent model motor vehicles not to exceed 20 mg as per the BleedEmissions Test Procedure (BETP). The California BETP is performed asdescribed in the following steps. In step 1, the canister is loaded with40 to 80 grams per hour of fuel vapor (about 50/50 mixture with N₂ orair) to 2-gram breakthrough, and then purged with N₂ at 22.7 L/min for300 canister bed volume exchanges. Step 1 is repeated for a total of 10cycles. In step 2, the canister is loaded with 40 grams per hour ofbutane (50/50 mixture with N₂) to 2-gram breakthrough, and then purgedaccording to specifications from the original equipment manufacturerrepresentative of one drive cycle. In step 3, a fuel tank is filled to40% capacity, and is soaked for a minimum of 6 hours to a maximum of 72hours at about 65° F. In step 4, the canister is connected to the fueltank, and the tank load port is connected to the canister load with thepurge port capped. The canister is then soaked for a minimum of 12 hoursto a maximum of 36 hours at about 65° F. In step 5, the assembly iscycled between 65° F. and 105° F. with a 12 hour ramp time to completetwo diurnal cycles in 48 hours. The highest hydrocarbon emission of each24-hour period is then reported. Bleed emission traps are currentlyinstalled in such fuel canisters to achieve such low bleed emissionvalues. These traps are consisting of extruded carbon monoliths, and aremeant to absorb the 100-500 mg of emissions from the fuel canister inthe two-day diurnal cycle.

Previously disclosed is a method of limiting the hydrocarbon emissionsunder stringent DBL conditions by routing the fuel vapor through aninitial adsorbent volume and then at least one subsequent adsorbentvolume prior to venting to the atmosphere, wherein the initial adsorbentvolume has a higher adsorption capacity than the subsequent adsorbentvolume. See U.S. Pat. No. RE38,844.

Also previously disclosed is an evaporative emission control canistersystem device with high purge efficiency and moderate butane workingcapacity having an initial, and at least one subsequent, adsorbentvolume and with an effective butane working capacity (BWC) of less than3 g/dL, a g-total BWC of between 2 grams and 6 grams, and two-day DBLemissions of no more than 20 mg at no more than about 210 liters ofpurge, applied after a 40 g/hr butane loading step. See U.S. PatentApplication Pub. No. 2015/0275727.

The activated carbons used in current state-of-the-art evaporativeemission control canisters are generally obtained from natural sourcessuch as coal or agricultural byproducts, and typically have a surfacearea in the 1100-2200 m²/g range and a total pore volume in the 0.8-1.5cm³/g range. Notably, when the pore volume is plotted as a function ofpore radius, these activated carbons all have a peak just below 20Ångstroms (Å), with relatively little pore volume in the 30-80 Å range.

Stricter regulations on DBL emissions continue to prompt development ofimproved evaporative emission control systems, particularly for use invehicles with reduced purge volumes (i.e., hybrid vehicles). Suchvehicles may otherwise produce high DBL emissions due to lower purgefrequency, which equates to lower total purge volume and higher residualhydrocarbon heel. Accordingly, it is desirable to have an evaporativeemission control system with low DBL emissions despite low volume and/orinfrequent purge cycles. Further, despite previously disclosed devicesfor capturing evaporative hydrocarbon emissions from the fuel system,there remains a need for evaporative emission control systems with highefficiency to reduce space requirements and weight while furtherreducing the quantity of potential evaporative emissions under a varietyof conditions. Particularly desirable are evaporative emission controlarticles and systems with a lower heel-build.

SUMMARY OF THE INVENTION

A coated substrate adapted for hydrocarbon adsorption and an evaporativeemission control articles and systems comprising the coated substrateare provided. The disclosed coated substrates, articles and systems areuseful in controlling evaporative hydrocarbon emissions and may providelow diurnal breathing loss (DBL) emissions even under a low purgecondition. The coated substrates remove evaporative emissions generatedin an internal combustion engine and/or associated fuel sourcecomponents before the emissions can be released into the atmosphere. Thecoated substrates comprise activated carbons with novel pore-sizedistributions, providing a higher absorption capacity at low hydrocarbonconcentrations while maintaining low heel build over manyadsorption/desorption cycles, like state-of-the-art activated carbons.It has been surprisingly found that only a certain combination ofsurface area, pore volume distribution, and butane isotherm shape canqualify the coated carbon to meet the stringent emission regulations.Accordingly, in a first aspect is provided a coated substrate adaptedfor hydrocarbon adsorption, the coated substrate having at least onesurface, and a coating on the at least one surface, the coatingcomprising particulate carbon and a binder, wherein the particulatecarbon has a BET surface area of at least about 1300 m²/g, and at leastone of: (i) a butane affinity of greater than 60% at 5% butane; (ii) abutane affinity of greater than 35% at 0.5% butane; (iii) a microporevolume greater than about 0.2 ml/g and a mesopore volume greater thanabout 0.5 ml/g.

In some embodiments, the particulate carbon has an n-butane adsorptioncapacity of at least about 40 ml/g at about 3 mm Hg n-butane pressure.In some embodiments, the particulate carbon has an n-butane adsorptioncapacity of from about 40 ml/g to about 80 ml/g at about 3 mm Hgn-butane pressure. In some embodiments, the particulate carbon has ann-butane adsorption capacity of from about 40 ml/g, about 45 ml/g, about50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 mug to about 70 ml/g,about 75 ml/g, or about 80 mug at about 3 mm Hg n-butane pressure.

In some embodiments, the particulate carbon has a BET surface area offrom about 1300 m²/g to about 2500 m²/g. In some embodiments, theparticulate carbon has a BET surface area of from about 1400 m²/g toabout 1600 m²/g.

In some embodiments, the particulate carbon has a micropore volume isfrom about 0.20 ml/g to about 0.35 ml/g. In some embodiments, theparticulate carbon has a micropore volume is from about 0.20 ml/g, about0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0.32 ml/g, about 0.33ml/g, about 0.34 ml/g, or about 0.35 ml/g.

In some embodiments, the particulate carbon has a mesopore volume offrom about 0.5 mug to about 0.8 ml/g. In some embodiments, theparticulate carbon has a mesopore volume of from about 0.5 ml/g, about0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about0.75 ml/g, or about 0.8 ml/g. In certain specific embodiments, theparticulate carbon has a BET surface area of about 1400 m²/gram, amicropore volume of about 0.3 ml/g, and a mesopore volume of about 0.75ml/g.

In some embodiments, the substrate is selected from the group consistingof foams, monolithic materials, non-wovens, wovens, sheets, papers,twisted spirals, ribbons, structured media of extruded form, structuredmedia of wound form, structured media of folded form, structured mediaof pleated form, structured media of corrugated form, structured mediaof poured form, structured media of bonded form, and combinationsthereof. In some embodiments, the substrate is a monolith. In someembodiments, the monolith is a ceramic. In some embodiments, thesubstrate is a plastic. In some embodiments, the plastic is selectedfrom the group consisting of polypropylene, nylon-6, nylon-6,6, aromaticnylon, polysulfone, polyether sulfone, polybutylene terephthalate,polyphthalamide, polyoxymethylene, polycarbonate, polyvinylchloride,polyester, and polyurethane. In some embodiments, the substrate is anon-woven fabric. In some embodiments, the substrate is an extrudedmedia. In some embodiments, the extruded media is a honeycomb. In otherembodiments, the substrate is a foam. In some embodiments, the foam hasgreater than about 10 pores per inch. In some embodiments, the foam hasgreater than about 20 pores per inch. In some embodiments, the foam hasbetween about 15 and about 40 pores per inch. In some embodiments, thefoam is a polyurethane. In some embodiments, the polyurethane is apolyether or polyester. In some embodiments, the foam is a reticulatedpolyurethane.

In some embodiments, the coating thickness is less than about 500microns.

In some embodiments, the binder is present in an amount from about 10%to about 50% by weight relative to the particulate carbon. In someembodiments, the binder is an organic polymer. In some embodiments, thebinder is an acrylic/styrene copolymer latex.

In another aspect is provided a bleed emission scrubber, the scrubbercomprising an adsorbent volume comprising a coated substrate adapted forhydrocarbon adsorption, the coated substrate comprising a substratehaving at least one surface, and a coating on the at least one surface,the coating comprising particulate carbon and a binder, wherein theparticulate carbon has a BET surface area of at least about 1300m²/gram; and at least one of: (i) a butane affinity of greater than 60%at 5% butane; (ii) a butane affinity of greater than 35% at 0.5% butane;(iii) a micropore volume greater than about 0.2 ml/g and a mesoporevolume greater than about 0.5 ml/g.

In some embodiments, the particulate carbon has an n-butane adsorptioncapacity of at least about 40 ml/g at about 3 mm Hg n-butane pressure.In some embodiments, the particulate carbon has an n-butane adsorptioncapacity of from about 40 ml/g to about 80 ml/g at about 3 mm Hgn-butane pressure. In some embodiments, the particulate carbon has ann-butane adsorption capacity of from about 40 ml/g, about 45 ml/g, about50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g to about 70ml/g, about 75 ml/g, or about 80 mug at about 3 mm Hg n-butane pressure.

In some embodiments, the particulate carbon has a BET surface area offrom about 1300 m²/g to about 2100 m²/g. In some embodiments, theparticulate carbon has a BET surface area of from about 1400 m²/g toabout 1600 m²/g. In some embodiments, the particulate carbon has amicropore volume is from about 0.20 ml/g to about 0.35 ml/g.

In some embodiments, the particulate carbon has a micropore volume isfrom about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g,about 0.24 ml/g, or about 0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g,about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g,about 0.32 ml/g, about 0.33 ml/g, about 0.34 ml/g, or about 0.35 ml/g.

In some embodiments, the particulate carbon has a mesopore volume offrom about 0.5 mug to about 0.8 ml/g. In some embodiments, theparticulate carbon has a mesopore volume of from about 0.5 ml/g, about0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about0.75 ml/g, or about 0.8 ml/g. In certain specific embodiments, theparticulate carbon has a BET surface area of about 1400 m²/g, amicropore volume of about 0.3 ml/g, and a mesopore volume of about 0.75ml/g.

In some embodiments, the adsorbent volume has a g-total butane workingcapacity (BWC) of less than about 2 grams. In some embodiments, theadsorbent volume has a g-total BWC of from about 0.2 grams to about 1.6grams.

In some embodiments, the substrate is selected from the group consistingof foams, monolithic materials, non-wovens, wovens, sheets, papers,twisted spirals, ribbons, structured media of extruded form, structuredmedia of wound form structured media of folded form, structured media ofpleated form, structured media of corrugated form, structured media ofpoured form, structured media of bonded form, and combinations thereof.In some embodiments, the substrate is a monolith. In some embodiments,the monolith is a ceramic. In some embodiments, the substrate is aplastic. In some embodiments, the plastic is selected from the groupconsisting of polypropylene, nylon-6, nylon-6,6, aromatic nylon,polysulfone, polyether sulfone, polybutylene terephthalate,polyphthalamide, polyoxymethylene, polycarbonate, polyvinylchloride,polyester, and polyurethane.

In some embodiments, the coating thickness is less than about 500microns.

In some embodiments, the binder is present in an amount from about 10%to about 50% by weight relative to the particulate carbon. In someembodiments, the binder is an organic polymer. In some embodiments, thebinder is an acrylic/styrene copolymer latex.

In a further aspect is provided an evaporative emission control canistersystem comprising a first adsorbent volume contained within a firstcanister, a fuel vapor purge tube for connecting the first canister toan engine, a fuel vapor inlet conduit for venting the fuel tank to thefirst canister, and a vent conduit for venting the first canister to theatmosphere and for admission of purge air to the first canister; and asecond adsorbent volume comprising the bleed emission scrubber asdisclosed herein; wherein the second adsorbent volume is in fluidcommunication with the first adsorbent volume, the bleed emissionscrubber being contained within the first canister or contained within asecond canister; and wherein the evaporative emission control canistersystem is configured to permit sequential contact of the first adsorbentvolume and the second adsorbent volume by the fuel vapor.

In some embodiments, the particulate carbon has an n-butane adsorptioncapacity of at least about 40 ml/g at about 3 mm Hg n-butane pressure.In some embodiments, the particulate carbon has an n-butane adsorptioncapacity of from about 40 ml/g to about 80 ml/g at about 3 mm Hgn-butane pressure. In some embodiments, the particulate carbon has ann-butane adsorption capacity of from about 40 ml/g, about 45 ml/g, about50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g to about 70ml/g, about 75 ml/g, or about 80 mug at about 3 mm Hg n-butane pressure.

In some embodiments, the particulate carbon has a BET surface area offrom about 1300 m²/g to about 2500 m²/g. In some embodiments, theparticulate carbon has a BET surface area of from about 1400 m²/g toabout 1600 m²/g.

In some embodiments, the particulate carbon has a micropore volume isfrom about 0.20 ml/g to about 0.35 ml/g. In some embodiments, theparticulate carbon has a micropore volume is from about 0.20 ml/g, about0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0.32 m/g, about 0.33ml/g, about 0.34 ml/g, or about 0.35 ml/g.

In some embodiments, the particulate carbon has a mesopore volume offrom about 0.5 ml/g to about 0.8 ml/g. In some embodiments, theparticulate carbon has a mesopore volume of from about 0.5 ml/g, about0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about0.75 ml/g, or about 0.8 ml/g. In certain specific embodiments, theparticulate carbon has a BET surface area of about 1400 m²/gram, amicropore volume of about 0.3 ml/g, and a mesopore volume of about 0.7ml/g.

In some embodiments, the bleed emission scrubber is contained in thefirst canister.

In some embodiments, the bleed emission scrubber is contained in thesecond canister.

In some embodiments, the second adsorbent volume has an effective butaneworking capacity (BWC) of less than about 3 g/dL, and a g-total BWC ofless than about 2 grams. In some embodiments, the second adsorbentvolume has a g-total BWC of from about 0.2 grams to about 1.999 grams.In some embodiments, the second adsorbent volume further comprises athird adsorbent volume, the third adsorbent volume having a g-total BWCof at least about 0.05 grams.

In some embodiments, the substrate is selected from the group consistingof foams, monolithic materials, non-wovens, wovens, sheets, papers,twisted spirals, ribbons, structured media of extruded form, structuredmedia of wound form structured media of folded form, structured media ofpleated form, structured media of corrugated form, structured media ofpoured form, structured media of bonded form, and combinations thereof.In some embodiments, the substrate is a monolith. In some embodiments,the monolith is a ceramic. In some embodiments, the substrate is aplastic. In some embodiments, the plastic is selected from the groupconsisting of polypropylene, nylon-6, nylon-6,6, aromatic nylon,polysulfone, polyether sulfone, polybutylene terephthalate,polyphthalamide, polyoxymethylene, polycarbonate, polyvinylchloride,polyester, and polyurethane.

In some embodiments, the coating thickness is less than about 500microns.

In some embodiments, the binder is present in an amount from about 10%to about 50% by weight relative to the particulate carbon. In someembodiments, the binder is an organic polymer. In some embodiments, thebinder is an acrylic/styrene copolymer latex.

In some embodiments, the third adsorbent volume comprises a reticulatedpolyurethane foam.

In some embodiments, the evaporative emission control canister systemhas a first adsorbent volume of from about 1.9 to about 3.0 liters andexhibits a 2-Day Diurnal Breathing Loss (DBL) that is less than about 20mg under the California Bleed Emission Test Protocol (BETP) when testedunder the following test conditions: i. the first adsorbent volume is2.5 L, and at a purge volume of 80 bed volumes; or ii. the firstadsorbent volume is 1.9 L, and at a purge volume of 135 bed volumes.

In some embodiments, the second absorbent volume has a g-total BWC ofless than about 2 grams, while the evaporative emission control canistermaintains a 2-day DBL that is less than about 20 mg under the CaliforniaBETP.

In a still further aspect is provided an evaporative emission controlsystem as disclosed herein, the system further comprising a fuel tankfor fuel storage; and an internal combustion engine adapted to consumethe fuel; wherein the evaporative emission control system is defined bya fuel vapor flow path from the fuel vapor inlet conduit to the firstcanister, toward the second adsorbent volume and to the vent conduit,and by a reciprocal air flow path from the vent conduit to the secondadsorbent volume, toward the first canister, and toward the fuel vaporpurge tube.

In some embodiments, the particulate carbon has an n-butane adsorptioncapacity of at least about 40 ml/g at about 3 mm Hg n-butane pressure.In some embodiments, the particulate carbon has an n-butane adsorptioncapacity of from about 40 ml/g to about 80 ml/g at about 3 mm Hgn-butane pressure. In some embodiments, the particulate carbon has ann-butane adsorption capacity of from about 40 ml/g, about 45 ml/g, about50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g to about 70ml/g, about 75 ml/g, or about 80 mug at about 3 mm Hg n-butane pressure.

In some embodiments, the particulate carbon has a BET surface area offrom about 1300 m²/g to about 2100 m²/g. In some embodiments, theparticulate carbon has a BET surface area of from about 1400 m²/g toabout 1600 m²/g.

In some embodiments, the particulate carbon has a micropore volume isfrom about 0.20 ml/g to about 0.35 ml/g. In some embodiments, theparticulate carbon has a micropore volume is from about 0.20 ml/g, about0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0.32 ml/g, about 0.33ml/g, about 0.34 ml/g, or about 0.35 ml/g.

In some embodiments, the particulate carbon has a mesopore volume offrom about 0.5 mug to about 0.8 ml/g. In some embodiments, theparticulate carbon has a mesopore volume of from about 0.5 ml/g, about0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about0.75 ml/g, or about 0.8 ml/g. In certain specific embodiments, theparticulate carbon has a BET surface area of about 1400 m²/gram, amicropore volume of about 0.3 ml/g, and a mesopore volume of about 0.7ml/g.

In some embodiments, the bleed emission scrubber is contained in thefirst canister. In some embodiments, the bleed emission scrubber iscontained in the second canister.

In some embodiments, the second adsorbent volume has an effective butaneworking capacity (BWC) of less than about 3 g/dL, and a g-total BWC ofless than about 2 grams. In some embodiments, the second adsorbentvolume has a g-total BWC of from about 0.2 grams to about 1.999 grams.In some embodiments, the second adsorbent volume further comprises athird adsorbent volume, the third adsorbent volume having a g-total BWCof at least about 0.05 grams.

In some embodiments, the substrate is selected from the group consistingof foams, monolithic materials, non-wovens, wovens, sheets, papers,twisted spirals, ribbons, structured media of extruded form, structuredmedia of wound form structured media of folded form, structured media ofpleated form, structured media of corrugated form, structured media ofpoured form, structured media of bonded form, and combinations thereof.In some embodiments, the substrate is a monolith. In some embodiments,the monolith is a ceramic. In some embodiments, the substrate is aplastic. In some embodiments, the plastic is selected from the groupconsisting of polypropylene, nylon-6, nylon-6,6, aromatic nylon,polysulfone, polyether sulfone, polybutylene terephthalate,polyphthalamide, polyoxymethylene, polycarbonate, polyvinylchloride,polyester, and polyurethane.

In some embodiments, the coating thickness is less than about 500microns.

In some embodiments, the binder is present in an amount from about 10%to about 50% by weight relative to the particulate carbon. In someembodiments, the binder is an organic polymer. In some embodiments, thebinder is an acrylic/styrene copolymer latex.

In some embodiments, the third adsorbent volume comprises a reticulatedpolyurethane foam.

In some embodiments, the first adsorbent volume is from about 1.9 toabout 3.0 liters, and the 2-Day Diurnal Breathing Loss (DBL) is lessthan about 20 mg under the California Bleed Emission Test Protocol(BETP) when tested under the following test conditions: i. the firstadsorbent volume is 2.5 L, and at a purge volume of 80 bed volumes; orii. the first adsorbent volume is 1.9 L, and at a purge volume of 135bed volumes.

In a still further aspect is provided an evaporative emission controlcanister system comprising an evaporative emission control canistercomprising at least one canister adsorbent volume comprising a canisteradsorbent material, and at least one bleed emission scrubber; whereinthe at least one bleed emission scrubber comprises a scrubber adsorbentvolume, wherein the scrubber adsorbent volume comprises a scrubberadsorbent material and has a g-total BWC of less than about 2 grams;wherein the bleed emission scrubber is in fluid communication with theevaporative emission control canister; wherein the evaporative emissioncontrol canister is configured to permit sequential contact of thecanister adsorbent volume and the scrubber adsorbent volume by the fuelvapor; and wherein the evaporative emission control canister system hasa 2-Day Diurnal Breathing Loss (DBL) of less than about 20 mg under theCalifornia Bleed Emission Test Protocol (BETP) when tested under thefollowing test conditions: i. the first adsorbent volume is 2.5 L, andat a purge volume of 80 bed volumes; or ii. the first adsorbent volumeis 1.9 L, and at a purge volume of 135 bed volumes.

In some embodiments, the evaporative emission control canister systemfurther comprises a fuel vapor purge tube for connecting the evaporativeemission control canister system to an engine, a fuel vapor inletconduit for venting the fuel tank to the evaporative emission controlcanister, and a vent conduit for venting the evaporative emissioncontrol canister to the atmosphere and for admission of purge air to theevaporative emission control canister.

In some embodiments, the canister adsorbent material is selected fromthe group consisting of activated carbon, carbon charcoal, zeolites,clays, porous polymers, porous alumina, porous silica, molecular sieves,kaolin, titania, ceria, and combinations thereof. In some embodiments,the activated carbon is derived from a material including a memberselected from the group consisting of wood, wood dust, wood flour,cotton linters, peat, coal, coconut, lignite, carbohydrates, petroleumpitch, petroleum coke, coal tar pitch, fruit pits, fruit stones, nutshells, nut pits, sawdust, palm, vegetables, synthetic polymer, naturalpolymer, lignocellulosic material, and combinations thereof.

In some embodiments, the scrubber adsorbent material comprises aparticulate carbon, wherein the particulate carbon has a BET surfacearea of at least about 1300 m²/g; and at least one of: (i) a butaneaffinity of greater than 60% at 5% butane; (ii) a butane affinity ofgreater than 35% at 0.5% butane; (iii) a micropore volume greater thanabout 0.2 ml/g and a mesopore volume greater than about 0.5 ml/g.

In some embodiments, the particulate carbon has an n-butane adsorptioncapacity of at least about 40 ml/g at about 3 mm Hg n-butane pressure.In some embodiments, the particulate carbon has an n-butane adsorptioncapacity of from about 40 ml/g to about 80 ml/g at about 3 mm Hgn-butane pressure. In some embodiments, the particulate carbon has ann-butane adsorption capacity of from about 40 ml/g, about 45 ml/g, about50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g to about 70ml/g, about 75 ml/g, or about 80 mug at about 3 mm Hg n-butane pressure.

In some embodiments, the particulate carbon has a BET surface area offrom about 1300 m²/g to about 2500 m²/g. In some embodiments, theparticulate carbon has a BET surface area of from about 1400 m²/g toabout 1600 m²/g.

In some embodiments, the particulate carbon has a micropore volume offrom about 0.20 mug to about 0.35 ml/g. In some embodiments, theparticulate carbon has a micropore volume of from about 0.20 ml/g, about0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0.32 ml/g, about 0.33ml/g, about 0.34 ml/g, or about 0.35 ml/g.

In some embodiments, the particulate carbon has a mesopore volume offrom about 0.5 mug to about 0.8 ml/g. In some embodiments, theparticulate carbon has a mesopore volume of from about 0.5 ml/g, about0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about0.75 ml/g, or about 0.8 ml/g.

In some embodiments, the particulate carbon has a BET surface area ofabout 1400 m²/gram, a micropore volume of about 0.3 ml/g, and a mesoporevolume of about 0.75 ml/g.

In some embodiments, the bleed emissions scrubber comprises a substrate.In some embodiments, the substrate is selected from the group consistingof foams, monolithic materials, non-wovens, wovens, sheets, papers,twisted spirals, ribbons, structured media of extruded form, structuredmedia of wound form structured media of folded form, structured media ofpleated form, structured media of corrugated form, structured media ofpoured form, structured media of bonded form, and combinations thereof.In some embodiments, the substrate is molded, formed or extruded with amixture comprising the scrubber adsorbent material. In some embodiments,the substrate comprises a coating, wherein the coating comprises thescrubber adsorbent material and a binder. In some embodiments, thesubstrate is a monolith. In some embodiments, the monolith is a ceramic.In some embodiments, the substrate is a plastic. In some embodiments,the plastic is selected from the group consisting of polypropylene,nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyether sulfone,polybutylene terephthalate, polyphthalamide, polyoxymethylene,polycarbonate, polyvinylchloride, polyester, and polyurethane.

In some embodiments, the coating thickness is less than about 500microns.

In some embodiments, the binder is present in an amount from about 10%to about 50% by weight relative to the particulate carbon. In someembodiments, the binder is an organic polymer. In some embodiments, thebinder is an acrylic/styrene copolymer latex.

In some embodiments, the second adsorbent volume has an effective BWC ofless than about 2 grams/dl. In some embodiments, the second adsorbentvolume has an effective BWC of from about 0.5 grams/dl to about 2grams/dl. In some embodiments, the second adsorbent volume has aneffective BWC of from about 0.5, about 0.6, about 0.7, about 0.8, orabout 0.9 to about 1.0, about 1.1, about 1.2, about 1.3, about 1.4,about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, or about 2.0grams/dL. In some embodiments, the second adsorbent volume has a g-totalBWC from about 0.1 grams to less than about 2 grams. In someembodiments, the second adsorbent volume has a g-total BWC of from about0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7,about 0.8, or about 0.9, to about 1.0, about 1.1, about 1.2, about 1.3,about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, or about 1.9grams.

In some embodiments, the evaporative emission control canister has acanister adsorbent volume of 3.5 L or less, 3.0 L or less, 2.5 L orless, or 2.0 L or less.

In some embodiments, the evaporative emission control canister systemcomprises a single canister adsorbent volume, wherein the canisteradsorbent volume comprises at least one chamber, wherein there iscanister adsorbent material loaded within the at least one chamber; asingle bleed emission scrubber, wherein the at least one bleed emissionscrubber comprises a scrubber adsorbent volume, wherein the scrubberadsorbent volume comprises a scrubber adsorbent material and has ag-total BWC of less than about 2 grams; a canister adsorbent volume offrom about 1.5 L to about 2.0 L; wherein the evaporative emissioncontrol canister has a 2-Day Diurnal Breathing Loss (DBL) of less thanabout 20 mg under the California Bleed Emission Test Protocol (BETP) ata purge volume of 135 bed volumes.

In some embodiments, the evaporative emission control canister systemhas a 2-Day DBL of less than about 10 mg under the BETP.

In some embodiments, the evaporative emission control canister systemcomprises a single canister adsorbent volume, wherein the canisteradsorbent volume comprises at least one chamber, wherein there iscanister adsorbent material loaded within the at least one chamber; asingle bleed emission scrubber; and a canister adsorbent volume of fromabout 2.5 L to about 3.0 L; the evaporative emission control canistersystem having a 2-Day Diurnal Breathing Loss (DBL) of less than about 20mg under the California Bleed Emission Test Protocol (BETP) at a purgevolume of 80 bed volumes. In some embodiments, the evaporative emissioncontrol canister has a 2-Day DBL of less than about 10 mg under the BETPat a purge volume of 80 bed volumes.

In some embodiments, the canister adsorbent volume comprises twochambers, wherein there is canister adsorbent material loaded withineach chamber. In some embodiments, the second adsorbent volume has aneffective BWC of less than about 2 grams/dl. In some embodiments, thesecond adsorbent volume has an effective BWC of from about 0.5 grams/dlto about 2 grams/dl. In some embodiments, the second adsorbent volumehas an effective BWC of from about 0.5, about 0.6, about 0.7, about 0.8,or about 0.9 to about 1.0, about 1.1, about 1.2, about 1.3, about 1.4,about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, or about 2.0grams/dL. In some embodiments, the second adsorbent volume has a g-totalBWC from about 0.1 grams to less than about 2 grams. In someembodiments, the second adsorbent volume has a g-total BWC of from about0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7,about 0.8, or about 0.9, to about 1.0, about 1.1, about 1.2, about 1.3,about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, or about 1.9grams.

The present disclosure includes, without limitation, the followingembodiments.

Embodiment 1

A coated substrate adapted for hydrocarbon adsorption comprising asubstrate having at least one surface, and a coating on the at least onesurface, the coating comprising particulate carbon and a binder, whereinthe particulate carbon has a BET surface area of at least about 1300m²/g; and at least one of: (i) a butane affinity of greater than 60% at5% butane; (ii) a butane affinity of greater than 35% at 0.5% butane;(iii) a micropore volume greater than about 0.2 ml/g and a mesoporevolume greater than about 0.5 ml/g.

Embodiment 2

The coated substrate of the preceding embodiment, wherein theparticulate carbon has an n-butane adsorption capacity of at least about40 mug at about 3 mm Hg n-butane pressure.

Embodiment 3

The coated substrate of any preceding embodiment, wherein theparticulate carbon has an n-butane adsorption capacity of from about 40ml/g to about 80 ml/g at about 3 mm Hg n-butane pressure.

Embodiment 4

The coated substrate of any preceding embodiment, wherein theparticulate carbon has an n-butane adsorption capacity of from about 40ml/g, about 45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, orabout 65 ml/g to about 70 ml/g, about 75 ml/g, or about 80 ml/g at about3 mm Hg n-butane pressure.

Embodiment 5

The coated substrate of any preceding embodiment, wherein theparticulate carbon has a BET surface area of from about 1300 m²/g toabout 2100 m²/g.

Embodiment 6

The coated substrate of any preceding embodiment, wherein theparticulate carbon has a BET surface area of from about 1400 m²/g toabout 1600 m²/g.

Embodiment 7

The coated substrate of any preceding embodiment, wherein theparticulate carbon has a micropore volume is from about 0.20 ml/g toabout 0.35 ml/g.

Embodiment 8

The coated substrate of any preceding embodiment, wherein theparticulate carbon has a micropore volume is from about 0.20 ml/g, about0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about0.25 mug to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0.32 ml/g, about 0.33ml/g, about 0.34 ml/g, or about 0.35 ml/g.

Embodiment 9

The coated substrate of any preceding embodiment, wherein theparticulate carbon has a mesopore volume of from about 0.5 ml/g to about0.8 ml/g.

Embodiment 10

The coated substrate of any preceding embodiment, wherein theparticulate carbon has a mesopore volume of from about 0.5 ml/g, about0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about0.75 ml/g, or about 0.8 ml/g.

Embodiment 11

The coated substrate of any preceding embodiment, wherein theparticulate carbon has a BET surface area of about 1400 m²/g, amicropore volume of about 0.3 ml/g, and a mesopore volume of about 0.75ml/g.

Embodiment 12

The coated substrate of any preceding embodiment, wherein the substrateis selected from the group consisting of foams, monolithic materials,non-wovens, wovens, sheets, papers, twisted spirals, ribbons, structuredmedia of extruded form, structured media of wound form structured mediaof folded form, structured media of pleated form, structured media ofcorrugated form, structured media of poured form, structured media ofbonded form, and combinations thereof.

Embodiment 13

The coated substrate of any preceding embodiment, wherein the substrateis a monolith.

Embodiment 14

The coated substrate of any preceding embodiment, wherein the monolithis a ceramic.

Embodiment 15

The coated substrate of any preceding embodiment, wherein the substrateis a plastic.

Embodiment 16

The coated substrate of any preceding embodiment, wherein the plastic isselected from the group consisting of polypropylene, nylon-6, nylon-6,6,aromatic nylon, polysulfone, polyether sulfone, polybutyleneterephthalate, polyphthalamide, polyoxymethylene, polycarbonate,polyvinylchloride, polyester, and polyurethane.

Embodiment 17

The coated substrate of any preceding embodiment, wherein the coatingthickness is less than about 500 microns.

Embodiment 18

The coated substrate of any preceding embodiment, wherein the binder ispresent in an amount from about 10% to about 50% by weight relative tothe particulate carbon.

Embodiment 19

The coated substrate of any preceding embodiment, wherein the binder isan organic polymer.

Embodiment 20

The coated substrate of any preceding embodiment, wherein the binder isan acrylic/styrene copolymer latex.

Embodiment 21

A bleed emission scrubber, the scrubber comprising an adsorbent volumecomprising a coated substrate adapted for hydrocarbon adsorption, thecoated substrate comprising at least one surface, and a coating on theat least one surface, the coating comprising particulate carbon and abinder, wherein the particulate carbon has a BET surface area of atleast about 1300 m²/g; and at least one of: (i) a butane affinity ofgreater than 60% at 5% butane; (ii) a butane affinity of greater than35% at 0.5% butane; (iii) a micropore volume greater than about 0.2 ml/gand a mesopore volume greater than about 0.5 ml/g.

Embodiment 22

The bleed emission scrubber of any preceding embodiment, wherein theparticulate carbon has an n-butane adsorption capacity of at least about40 ml/g at about 3 mm Hg n-butane pressure.

Embodiment 23

The bleed emission scrubber of any preceding embodiment, wherein theparticulate carbon has an n-butane adsorption capacity of from about 40ml/g to about 80 ml/g at about 3 mm Hg n-butane pressure.

Embodiment 24

The bleed emission scrubber of any preceding embodiment, wherein theparticulate carbon has an n-butane adsorption capacity of from about 40ml/g, about 45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, orabout 65 ml/g to about 70 ml/g, about 75 ml/g, or about 80 ml/g at about3 mm Hg n-butane pressure.

Embodiment 25

The bleed emission scrubber of any preceding embodiment, wherein theparticulate carbon has a BET surface area of from about 1300 m²/g toabout 2100 m²/g.

Embodiment 26

The bleed emission scrubber of any preceding embodiment, wherein theparticulate carbon has a BET surface area of from about 1400 m²/g toabout 1600 m²/g.

Embodiment 27

The bleed emission scrubber of any preceding embodiment, wherein theparticulate carbon has a micropore volume is from about 0.20 ml/g toabout 0.35 ml/g.

Embodiment 28

The bleed emission scrubber of any preceding embodiment, wherein theparticulate carbon has a micropore volume is from about 0.20 ml/g, about0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0.32 ml/g, about 0.33ml/g, about 0.34 ml/g, or about 0.35 ml/g.

Embodiment 29

The bleed emission scrubber of any preceding embodiment, wherein theparticulate carbon has a mesopore volume of from about 0.5 ml/g to about0.8 ml/g.

Embodiment 30

The bleed emission scrubber of any preceding embodiment, wherein theparticulate carbon has a mesopore volume of from about 0.5 ml/g, about0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about0.75 ml/g, or about 0.8 ml/g.

Embodiment 31

The bleed emission scrubber of any preceding embodiment, wherein theparticulate carbon has a BET surface area of about 1400 m²/g, amicropore volume of about 0.3 ml/g, and a mesopore volume of about 0.75ml/g.

Embodiment 32

The bleed emission scrubber of any preceding embodiment, wherein theadsorbent volume has a g-total butane working capacity (BWC) of lessthan about 2 grams.

Embodiment 33

The bleed emission scrubber of any preceding embodiment, wherein theadsorbent volume has a g-total BWC of from about 0.2 grams to about 1.6grams.

Embodiment 34

The bleed emission scrubber of any preceding embodiment, wherein thesubstrate is selected from the group consisting of foams, monolithicmaterials, non-wovens, wovens, sheets, papers, twisted spirals, ribbons,structured media of extruded form, structured media of wound formstructured media of folded form, structured media of pleated form,structured media of corrugated form, structured media of poured form,structured media of bonded form, and combinations thereof.

Embodiment 35

The bleed emission scrubber of any preceding embodiment, wherein thesubstrate is a monolith.

Embodiment 36

The bleed emission scrubber of any preceding embodiment, wherein themonolith is a ceramic.

Embodiment 37

The bleed emission scrubber of any preceding embodiment, wherein thesubstrate is a plastic.

Embodiment 38

The bleed emission scrubber of any preceding embodiment, wherein theplastic is selected from the group consisting of polypropylene, nylon-6,nylon-6,6, aromatic nylon, polysulfone, polyether sulfone, polybutyleneterephthalate, polyphthalamide, polyoxymethylene, polycarbonate,polyvinylchloride, polyester, and polyurethane.

Embodiment 39

The bleed emission scrubber of any preceding embodiment, wherein thecoating thickness is less than about 500 microns.

Embodiment 40

The bleed emission scrubber of any preceding embodiment, wherein thebinder is present in an amount from about 10% to about 50% by weightrelative to the particulate carbon.

Embodiment 41

The bleed emission scrubber of any preceding embodiment, wherein thebinder is an organic polymer.

Embodiment 42

The bleed emission scrubber of any preceding embodiment, wherein thebinder is an acrylic/styrene copolymer latex.

Embodiment 43

An evaporative emission control canister system comprising a firstadsorbent volume contained within a first canister, a fuel vapor purgetube for connecting the first canister to an engine, a fuel vapor inletconduit for venting the fuel tank to the first canister, and a ventconduit for venting the first canister to the atmosphere and foradmission of purge air to the first canister; and a second adsorbentvolume comprising the bleed emission scrubber of any previousembodiment; wherein the second adsorbent volume is in fluidcommunication with the first adsorbent volume, the bleed emissionscrubber being contained within the first canister or contained within asecond canister; and wherein the evaporative emission control system isconfigured to permit sequential contact of the first adsorbent volumeand the second adsorbent volume by the fuel vapor.

Embodiment 44

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has an n-butane adsorptioncapacity of at least about 40 ml/g at about 3 mm Hg n-butane pressure.

Embodiment 45

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has an n-butane adsorptioncapacity of from about 40 mug to about 80 ml/g at about 3 mm Hg n-butanepressure.

Embodiment 46

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has an n-butane adsorptioncapacity of from about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55ml/g, about 60 ml/g, or about 65 ml/g to about 70 ml/g, about 75 ml/g,or about 80 mug at about 3 mm Hg n-butane pressure.

Embodiment 47

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has a BET surface area offrom about 1300 m²/g to about 2100 m²/g.

Embodiment 48

The evaporative emission control system of any preceding embodiment,wherein the particulate carbon has a BET surface area of from about 1400m²/g to about 1600 m²/g.

Embodiment 49

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has a micropore volume isfrom about 0.20 ml/g to about 0.35 ml/g.

Embodiment 50

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has a micropore volume isfrom about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g,about 0.24 ml/g, or about 0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g,about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g,about 0.32 ml/g, about 0.33 ml/g, about 0.34 ml/g, or about 0.35 ml/g.

Embodiment 51

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has a mesopore volume of fromabout 0.5 ml/g to about 0.8 ml/g.

Embodiment 52

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has a mesopore volume of fromabout 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g,about 0.70 ml/g, about 0.75 ml/g, or about 0.8 ml/g.

Embodiment 53

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has a BET surface area ofabout 1400 m²/gram, a micropore volume of about 0.3 ml/g, and a mesoporevolume of about 0.7 ml/g.

Embodiment 54

The evaporative emission control canister system of any precedingembodiment, wherein the bleed emission scrubber is located within thefirst adsorbent volume of the evaporative emission control canister.

Embodiment 55

The evaporative emission control canister system of any precedingembodiment, wherein the bleed emission scrubber is located in a separatecanister that is in fluid communication with the evaporative emissioncontrol canister.

Embodiment 56

The evaporative emission control canister system of any precedingembodiment, wherein the second adsorbent volume has an effective butaneworking capacity (BWC) of less than about 3 g/dL, and a g-total BWC ofless than about 2 grams.

Embodiment 57

The evaporative emission control canister system of any precedingembodiment, wherein the second adsorbent volume has a g-total BWC offrom about 0.2 grams to about 1.999 grams.

Embodiment 58

The evaporative emission control system of any preceding embodiment,wherein the second adsorbent volume further comprises a third adsorbentvolume, the third adsorbent volume having a BWC of at least about 0.05grams.

Embodiment 59

The evaporative emission control canister system of any precedingembodiment, wherein the substrate is selected from the group consistingof foams, monolithic materials, non-wovens, wovens, sheets, papers,twisted spirals, ribbons, structured media of extruded form, structuredmedia of wound form structured media of folded form, structured media ofpleated form, structured media of corrugated form, structured media ofpoured form, structured media of bonded form, and combinations thereof.

Embodiment 60

The evaporative emission control canister system of any precedingembodiment, wherein the substrate is a monolith.

Embodiment 61

The evaporative emission control canister system of any precedingembodiment, wherein the monolith is a ceramic.

Embodiment 62

The evaporative emission control canister system of any precedingembodiment, wherein the substrate is a plastic.

Embodiment 63

The evaporative emission control canister system of any precedingembodiment, wherein the plastic is selected from the group consisting ofpolypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone,polyether sulfone, polybutylene terephthalate, polyphthalamide,polyoxymethylene, polycarbonate, polyvinylchloride, polyester, andpolyurethane.

Embodiment 64

The evaporative emission control canister system of any precedingembodiment, wherein the coating thickness is less than about 500microns.

Embodiment 65

The evaporative emission control canister system of any precedingembodiment, wherein the binder is present in an amount from about 10% toabout 50% by weight relative to the particulate carbon.

Embodiment 66

The evaporative emission control canister system of any precedingembodiment, wherein the binder is an organic polymer.

Embodiment 67

The evaporative emission control canister system of any precedingembodiment, wherein the binder is an acrylic/styrene copolymer latex.

Embodiment 68

The evaporative emission control canister system of any precedingembodiment, wherein the third adsorbent volume comprises a reticulatedpolyurethane foam.

Embodiment 69

The evaporative emission control canister system of any precedingembodiment, wherein the first adsorbent volume is from about 1.9 toabout 3.0 liters, and wherein the 2-Day Diurnal Breathing Loss (DBL) isless than about 20 mg under the California Bleed Emission Test Protocol(BETP) when tested under the following test conditions: i. the firstadsorbent volume is 2.5 L, and at a purge volume of 80 bed volumes; orii. the first adsorbent volume is 1.9 L, and at a purge volume of 135bed volumes.

Embodiment 70

The evaporative emission control canister system of any previousembodiment, the system further comprising: a fuel tank for fuel storage;and an internal combustion engine adapted to consume the fuel; whereinthe evaporative emission control system is defined by a fuel vapor flowpath from the fuel vapor inlet conduit to the first canister, toward thesecond adsorbent volume and to the vent conduit, and by a reciprocal airflow path from the vent conduit to the second adsorbent volume, towardthe first canister, and toward the fuel vapor purge tube.

Embodiment 71

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has an n-butane adsorptioncapacity of at least about 40 ml/g at about 3 mm Hg n-butane pressure.

Embodiment 72

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has an n-butane adsorptioncapacity of from about 40 mug to about 80 ml/g at about 3 mm Hg n-butanepressure.

Embodiment 73

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has an n-butane adsorptioncapacity of from about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55ml/g, about 60 ml/g, or about 65 ml/g to about 70 ml/g, about 75 ml/g,or about 80 mug at about 3 mm Hg n-butane pressure.

Embodiment 74

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has a BET surface area offrom about 1300 m²/g to about 2100 m²/g.

Embodiment 75

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has a BET surface area offrom about 1400 m²/g to about 1600 m²/g.

Embodiment 76

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has a micropore volume isfrom about 0.20 mug to about 0.35 ml/g.

Embodiment 77

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has a micropore volume isfrom about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g,about 0.24 ml/g, or about 0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g,about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g,about 0.32 ml/g, about 0.33 ml/g, about 0.34 ml/g, or about 0.35 ml/g.

Embodiment 78

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has a mesopore volume of fromabout 0.5 ml/g to about 0.8 ml/g.

Embodiment 79

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has a mesopore volume of fromabout 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g,about 0.70 ml/g, about 0.75 ml/g, or about 0.8 ml/g.

Embodiment 80

The evaporative emission control canister system of any precedingembodiment, wherein the particulate carbon has a BET surface area ofabout 1400 m²/gram, a micropore volume of about 0.3 ml/g, and a mesoporevolume of about 0.7 ml/g.

Embodiment 81

The evaporative emission control canister system of any precedingembodiment, wherein the bleed emission scrubber is contained in thefirst canister.

Embodiment 82

The evaporative emission control canister system of any precedingembodiment, wherein the bleed emission scrubber is contained in thesecond canister.

Embodiment 83

The evaporative emission control canister system of any precedingembodiment, wherein the second adsorbent volume has an effective butaneworking capacity (BWC) of less than about 3 g/dL, and a g-total BWC ofless than about 2 grams.

Embodiment 84

The evaporative emission control canister system of any precedingembodiment, wherein the second adsorbent volume has a g-total BWC offrom about 0.2 grams to about 1.999 grams.

Embodiment 85

The evaporative emission control canister system of any precedingembodiment, wherein the second adsorbent volume further comprises athird adsorbent volume, the third adsorbent volume having a g-total BWCof at least about 0.05 grams.

Embodiment 86

The evaporative emission control canister system of any precedingembodiment, wherein the substrate is selected from the group consistingof foams, monolithic materials, non-wovens, wovens, sheets, papers,twisted spirals, ribbons, structured media of extruded form, structuredmedia of wound form structured media of folded form, structured media ofpleated form, structured media of corrugated form, structured media ofpoured form, structured media of bonded form, and combinations thereof.

Embodiment 87

The evaporative emission control canister system of any precedingembodiment, wherein the substrate is a monolith.

Embodiment 88

The evaporative emission control canister system of any precedingembodiment, wherein the monolith is a ceramic.

Embodiment 89

The evaporative emission control canister system of any precedingembodiment, wherein the substrate is a plastic.

Embodiment 90

The evaporative emission control canister system of any precedingembodiment, wherein the plastic is selected from the group consisting ofpolypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone,polyether sulfone, polybutylene terephthalate, polyphthalamide,polyoxymethylene, polycarbonate, polyvinylchloride, polyester, andpolyurethane.

Embodiment 91

The evaporative emission control canister system of any precedingembodiment, wherein the coating thickness is less than about 500microns.

Embodiment 92

The evaporative emission control canister system of any precedingembodiment, wherein the binder is present in an amount from about 10% toabout 50% by weight relative to the particulate carbon.

Embodiment 93

The evaporative emission control canister system of any precedingembodiment, wherein the binder is an organic polymer.

Embodiment 94

The evaporative emission control canister system of any precedingembodiment, wherein the binder is an acrylic/styrene copolymer latex.

Embodiment 95

The evaporative emission control canister system of any precedingembodiment, wherein the third adsorbent volume comprises a reticulatedpolyurethane foam.

Embodiment 96

The evaporative emission control canister system of any precedingembodiment, wherein the first adsorbent volume is from about 1.9 toabout 3.0 liters, and wherein the 2-Day Diurnal Breathing Loss (DBL) isless than about 20 mg under the California Bleed Emission Test Protocol(BETP) when tested under the following test conditions: i. the firstadsorbent volume is 2.5 L, and at a 5 purge volume of 80 bed volumes; orii. the first adsorbent volume is 1.9 L, and at a purge volume of 135bed volumes.

Embodiment 97

The evaporative emission control canister system of any precedingembodiment, wherein the 2-Day DBL is less than about 20 mg under theCalifornia BETP, and wherein the second absorbent volume has a g-totalBWC of less than about 2 grams.

Embodiment 98

An evaporative emission control canister system comprising anevaporative emission control canister comprising at least one canisteradsorbent volume comprising a canister adsorbent material, and at leastone bleed emission scrubber; wherein the at least one bleed emissionscrubber comprises a scrubber adsorbent volume, wherein the scrubberadsorbent volume comprises a scrubber adsorbent material and has ag-total BWC of less than about 2 grams; wherein the bleed emissionscrubber is in fluid communication with the evaporative emission controlcanister; wherein the evaporative emission control canister isconfigured to permit sequential contact of the canister adsorbent volumeand the scrubber adsorbent volume by the fuel vapor; and wherein theevaporative emission control canister system has a 2-Day DiurnalBreathing Loss (DBL) of less than about 20 mg under the California BleedEmission Test Protocol (BETP) when tested under the following testconditions: a total canister adsorbent material volume in theevaporative emission control canister of 2.5 L and a purge volume of 80bed volumes.

Embodiment 99

The evaporative emission control canister system of the previousembodiment, further comprising a fuel vapor purge tube for connectingthe evaporative emission control canister to an engine, a fuel vaporinlet conduit for venting the fuel tank to the evaporative emissioncontrol canister, and a vent conduit for venting the evaporativeemission control canister to the atmosphere and for admission of purgeair to the evaporative emission control canister.

Embodiment 100

The evaporative emission control canister system of any previousembodiment, wherein the canister adsorbent material is selected from thegroup consisting of activated carbon, carbon charcoal, zeolites, clays,porous polymers, porous alumina, porous silica, molecular sieves,kaolin, titania, ceria, and combinations thereof.

Embodiment 101

The evaporative emission control canister system of any previousembodiment, wherein the activated carbon is derived from a materialincluding a member selected from the group consisting of wood, wooddust, wood flour, cotton linters, peat, coal, coconut, lignite,carbohydrates, petroleum pitch, petroleum coke, coal tar pitch, fruitpits, fruit stones, nut shells, nut pits, sawdust, palm, vegetables,synthetic polymer, natural polymer, lignocellulosic material, andcombinations thereof.

Embodiment 102

The evaporative emission control canister system of any previousembodiment, wherein the scrubber adsorbent material comprises aparticulate carbon, wherein the particulate carbon has a BET surfacearea of at least about 1300 m²/g; and at least one of: (i) a butaneaffinity of greater than 60% at 5% butane; (ii) a butane affinity ofgreater than 35% at 0.5% butane; (iii) a micropore volume greater thanabout 0.2 ml/g and a mesopore volume greater than about 0.5 ml/g.

Embodiment 103

The evaporative emission control canister system of any previousembodiment, wherein the particulate carbon has an n-butane adsorptioncapacity of at least about 40 ml/g at about 3 mm Hg n-butane pressure.

Embodiment 104

The evaporative emission control canister system of any previousembodiment, wherein the particulate carbon has an n-butane adsorptioncapacity of from about 40 mug to about 80 ml/g at about 3 mm Hg n-butanepressure.

Embodiment 105

The evaporative emission control canister system of any previousembodiment, wherein the particulate carbon has an n-butane adsorptioncapacity of from about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55ml/g, about 60 ml/g, or about 65 ml/g to about 70 ml/g, about 75 ml/g,or about 80 mug at about 3 mm Hg n-butane pressure.

Embodiment 106

The evaporative emission control canister system of any previousembodiment, wherein the particulate carbon has a BET surface area offrom about 1300 m²/g to about 2500 m²/g.

Embodiment 107

The evaporative emission control canister system of any previousembodiment, wherein the particulate carbon has a BET surface area offrom about 1400 m²/g to about 1600 m²/g.

Embodiment 108

The evaporative emission control canister system of any previousembodiment, wherein the particulate carbon has a micropore volume offrom about 0.20 ml/g to about 0.35 ml/g.

Embodiment 109

The evaporative emission control canister system of any previousembodiment, wherein the particulate carbon has a micropore volume offrom about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g,about 0.24 ml/g, or about 0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g,about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g,about 0.32 ml/g, about 0.33 ml/g, about 0.34 ml/g, or about 0.35 ml/g.

Embodiment 110

The evaporative emission control canister system of any previousembodiment, wherein the particulate carbon has a mesopore volume of fromabout 0.5 ml/g to about 0.8 ml/g.

Embodiment 111

The evaporative emission control canister system of any previousembodiment, wherein the particulate carbon has a mesopore volume of fromabout 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g,about 0.70 ml/g, about 0.75 ml/g, or about 0.8 ml/g.

Embodiment 112

The evaporative emission control canister system of any previousembodiment, wherein the particulate carbon has a BET surface area ofabout 1400 m²/gram, a micropore volume of about 0.3 ml/g, and a mesoporevolume of about 0.75 ml/g.

Embodiment 113

The evaporative emission control canister system of any previousembodiment, wherein the bleed emissions scrubber comprises a substrate.

Embodiment 114

The evaporative emission control canister system of any previousembodiment, wherein the substrate is selected from the group consistingof foams, monolithic materials, non-wovens, wovens, sheets, papers,twisted spirals, ribbons, structured media of extruded form, structuredmedia of wound form structured media of folded form, structured media ofpleated form, structured media of corrugated form, structured media ofpoured form, structured media of bonded form, and combinations thereof.

Embodiment 115

The evaporative emission control canister system of any previousembodiment, wherein the substrate is molded, formed or extruded with amixture comprising the scrubber adsorbent material.

Embodiment 116

The evaporative emission control canister system of any previousembodiment, wherein the substrate comprises a coating, wherein thecoating comprises the scrubber adsorbent material and a binder.

Embodiment 117

The evaporative emission control canister system of any previousembodiment, wherein the substrate is a monolith.

Embodiment 118

The evaporative emission control canister system of any previousembodiment, wherein the monolith is a ceramic.

Embodiment 119

The evaporative emission control canister system of any previousembodiment, wherein the substrate is a plastic.

Embodiment 120

The evaporative emission control canister system of any previousembodiment, wherein the plastic is selected from the group consisting ofpolypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone,polyether sulfone, polybutylene terephthalate, polyphthalamide,polyoxymethylene, polycarbonate, polyvinylchloride, polyester, andpolyurethane.

Embodiment 121

The evaporative emission control canister system of any previousembodiment, wherein the coating thickness is less than about 500microns.

Embodiment 122

The evaporative emission control canister system of any previousembodiment, wherein the binder is present in an amount from about 10% toabout 50% by weight relative to the particulate carbon.

Embodiment 123

The evaporative emission control canister system of any previousembodiment, wherein the binder is an organic polymer.

Embodiment 124

The evaporative emission control canister system of any previousembodiment, wherein the binder is an acrylic/styrene copolymer latex.

Embodiment 125

The evaporative emission control canister system of any previousembodiment, wherein the second adsorbent volume has an effective BWC ofless than about 2 grams/dl.

Embodiment 126

The evaporative emission control canister system of any previousembodiment, wherein the second adsorbent volume has an effective BWC offrom about 0.5 grams/dl to about 2 grams/dl.

Embodiment 127

The evaporative emission control canister system of any previousembodiment, wherein the second adsorbent volume has a g-total BWC fromabout 0.1 grams to less than about 2 grams.

Embodiment 128

The evaporative emission control canister system of any previousembodiment, wherein the evaporative emission control canister has acanister adsorbent volume of 3.5 L or less, 3.0 L or less, 2.5 L orless, or 2.0 L or less.

Embodiment 129

The evaporative emission control canister system of any previousembodiment, comprising a single canister adsorbent volume, wherein thecanister adsorbent volume comprises at least one chamber, wherein thereis canister adsorbent material loaded within the at least one chamber; asingle bleed emission scrubber, wherein the at least one bleed emissionscrubber comprises a scrubber adsorbent volume, wherein the scrubberadsorbent volume comprises a scrubber adsorbent material and has ag-total BWC of less than about 2 grams; a canister adsorbent volume offrom about 1.5 L to about 2.0 L; wherein the evaporative emissioncontrol canister has a 2-Day Diurnal Breathing Loss (DBL) of less thanabout 20 mg under the California Bleed Emission Test Protocol (BETP) ata purge volume of 135 bed volumes.

Embodiment 130

The evaporative emission control canister system of any previousembodiment, wherein the wherein the evaporative emission controlcanister has a 2-Day Diurnal Breathing Loss (DBL) of less than about 10mg under the California Bleed Emission Test Protocol (BETP) at a purgevolume of 135 bed volumes.

Embodiment 131

The evaporative emission control canister system of any previousembodiment, wherein the canister adsorbent volume comprises twochambers, wherein there is canister adsorbent material loaded withineach chamber.

Embodiment 132

The evaporative emission control canister system of any previousembodiment, wherein the second adsorbent volume has an effective BWC ofless than about 2 grams/dl.

Embodiment 133

The evaporative emission control canister system of any previousembodiment, wherein the second adsorbent volume has an effective BWC offrom about 0.5 grams/dl to about 2 grams/dl.

Embodiment 134

The evaporative emission control canister system of any previousembodiment, wherein the second adsorbent volume has a g-total BWC fromabout 0.1 grams to less than about 2 grams.

Embodiment 135

The evaporative emission control canister system of any previousembodiment, comprising a single canister adsorbent volume, wherein thecanister adsorbent volume comprises at least one chamber, wherein thereis canister adsorbent material loaded within the at least one chamber; asingle bleed emission scrubber; a canister adsorbent volume of fromabout 2.5 L to about 3.0 L; wherein the evaporative emission controlcanister has a 2-Day Diurnal Breathing Loss (DBL) of less than about 20mg under the California Bleed Emission Test Protocol (BETP) at a purgevolume of 80 bed volumes.

Embodiment 136

The evaporative emission control canister system of any previousembodiment, wherein the evaporative emission control canister has a2-Day Diurnal Breathing Loss (DBL) of less than about 10 mg under theCalifornia Bleed Emission Test Protocol (BETP) at a purge volume of 80bed volumes.

Embodiment 137

The evaporative emission control canister system of any previousembodiment, wherein the canister adsorbent volume comprises twochambers, wherein there is canister adsorbent material loaded withineach chamber.

Embodiment 138

The evaporative emission control canister system of any previousembodiment, wherein the second adsorbent volume has an effective BWC ofless than about 2 grams/dl.

Embodiment 139

The evaporative emission control canister system of any previousembodiment, wherein the second adsorbent volume has an effective BWC offrom about 0.5 grams/dl to about 2 grams/dl.

Embodiment 140

The evaporative emission control canister system of any previousembodiment, wherein the second adsorbent volume has a g-total BWC fromabout 0.1 grams to less than about 2 grams.

These and other features, aspects, and advantages of the disclosure willbe apparent from a reading of the following detailed descriptiontogether with the accompanying drawings, which are briefly describedbelow. The invention includes any combination of two, three, four, ormore of the above-noted embodiments as well as combinations of any two,three, four, or more features or elements set forth in this disclosure,regardless of whether such features or elements are expressly combinedin a specific embodiment description herein. This disclosure is intendedto be read holistically such that any separable features or elements ofthe disclosed invention, in any of its various aspects and embodiments,should be viewed as intended to be combinable unless the context clearlydictates otherwise. Other aspects and advantages of the presentinvention will become apparent from the following.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to provide an understanding of embodiments of the invention,reference is made to the appended drawings, in which reference numeralsrefer to components of exemplary embodiments of the invention. Thedrawings are exemplary only, and should not be construed as limiting theinvention. The disclosure described herein is illustrated by way ofexample and not by way of limitation in the accompanying figures. Forsimplicity and clarity of illustration, features illustrated in thefigures are not necessarily drawn to scale. For example, the dimensionsof some features may be exaggerated relative to other features forclarity. Further, where considered appropriate, reference labels havebeen repeated among the figures to indicate corresponding or analogouselements.

FIG. 1A is a cross-sectional view of a bleed emission scrubber providedaccording to a first embodiment;

FIG. 1B is a cross-sectional view of a bleed emission scrubber providedaccording to a second embodiment;

FIG. 1C is a cross-sectional view of a bleed emission scrubber providedaccording to a third embodiment:

FIG. 2 is a schematic representation of an evaporative emission controlsystem comprising an evaporative emission control canister and a bleedemission scrubber provided in accordance with one embodiment;

FIG. 3 is a cross-sectional view of a bleed emission scrubber providedaccording to a fourth embodiment;

FIG. 4 is a graph illustrating the cumulative pore volume measurementsat pore widths of 4-10 Å for several particulate carbons;

FIG. 5 is a graph illustrating the cumulative pore volume measurementsat pore widths of 1-30 Å for several particulate carbons;

FIGS. 6A, 6B, and 6C are graphs illustrating butane isotherms forseveral particulate carbons:

FIG. 6D is a graph illustrating butane adsorption for severalparticulate carbons:

FIGS. 6E and 6F are graphs illustrating butane affinity for severalparticulate carbons: and

FIG. 7 is a graph illustrating butane breakthrough curves for severalparticulate carbons.

DETAILED DESCRIPTION OF THE INVENTION

The present disclosure is aimed at a coated substrate adapted forhydrocarbon adsorption and an evaporative emission control articles andsystems comprising the coated substrate are provided. The disclosedcoated substrates, articles and systems are useful in controllingevaporative hydrocarbon emissions and may provide low diurnal breathingloss (DBL) emissions even under a low purge condition. The coatedsubstrates remove evaporative emissions generated in an internalcombustion engine and/or associated fuel source components before theemissions can be released into the atmosphere. The coated substratescomprise activated carbons with novel pore-size distributions, providinga higher adsorption capacity at relevant fugitive emissionconcentrations, and low heel build over many adsorption/desorptioncycles, as compared to state-of-the-art activated carbons. It has beensurprisingly found that only a certain combination of surface area, porevolume distribution, and butane isotherm shape can qualify the coatedcarbon to meet the stringent emission regulations.

The present invention now will be described more fully hereinafter. Thisinvention may, however, be embodied in many different forms and shouldnot be construed as limited to the embodiments set forth herein; rather,these embodiments are provided so that this disclosure will be thoroughand complete, and will fully convey the scope of the invention to thoseskilled in the art.

Definitions

Unless otherwise defined, all technical terms used herein have the samemeaning as commonly understood by one of ordinary skill in the art towhich this disclosure belongs.

The articles “a” and “an” herein refer to one or to more than one (e.g.at least one) of the grammatical object. Any ranges cited herein areinclusive. The term “about” used throughout is used to describe andaccount for small fluctuations. For instance, “about” may mean thenumeric value may be modified by ±5%, +4%, ±3%, ±2%, ±1%, ±0.5%, ±0.4%,±0.3%, ±0.2%, ±0.1% or ±0.05%. All numeric values are modified by theterm “about” whether or not explicitly indicated. Numeric valuesmodified by the term “about” include the specific identified value. Forexample “about 5.0” includes 5.0.

The term “adsorbent material,” as used herein, refers to an adsorbentmaterial or adsorbent containing material along vapor flow path, and mayconsist of a bed of particulate material, a monolith, honeycomb, sheetor other material.

The term “associated” means for instance “equipped with”, “connected to”or in “communication with”, for example “electrically connected” or in“fluid communication with” or otherwise connected in a way to perform afunction. The term “associated” may mean directly associated with orindirectly associated with, for instance through one or more otherarticles or elements.

The term “micropore volume” refers to the volume of pores within theparticulate carbon which have pore sizes of from about 0.3 nm to about 1nm.

The term “mesopore volume” refers to the volume of pores within theparticulate carbon which have pore sizes of from about 1 nm to about 30nm.

As used herein, the term “substrate” refers to the material onto whichthe adsorbent material is placed, typically in the form of a washcoat.

As used herein, the term “washcoat” has its usual meaning in the art ofa thin, adherent coating of a material applied to a substrate material.A washcoat is formed by preparing a slurry containing a specified solidscontent (e.g., 10-50% by weight) of adsorbent in a liquid, which is thencoated onto a substrate and dried to provide a washcoat layer.

The term “vehicle” means for instance any vehicle having an internalcombustion engine and includes for instance passenger automobiles, sportutility vehicles, minivans, vans, trucks, buses, refuse vehicles,freight trucks, construction vehicles, heavy equipment, militaryvehicles, farm vehicles and the like.

Unless otherwise indicated, all parts and percentages are by weight.“Weight percent (wt %),” if not otherwise indicated, is based on anentire composition free of any volatiles, that is, based on dry solidscontent.

Coating Compositions

The present coatings comprise particulate carbon and a binder.Particulate carbon is an activated carbon; activated carbon is a highlyporous carbon with a very large surface area, generally at least about400 m²/g. Activated carbon is well known in the art. See, e.g.,commonly-assigned U.S. Pat. No. 7,442,232. See also U.S. Pat. No.7,467,620.

Described herein is an activated particulate carbon material havingunique adsorption properties. When the pore volume of this particulatecarbon is plotted as a function of pore radius, in addition to a peakjust below 20 Å (2 nm), the present particulate carbon has a significantamount of pore volume in the 30-80 Å (3-8 nm) range. Without wishing tobe bound by theory, it is believed that this feature of additional porevolume in the 30-80 Å range imparts a lower heel build compared tostate-of-the-art activated carbons used for evaporative emission controlof hydrocarbons in automotive applications. This particulate carbon ismade from a synthetic resin precursor by a process which can produceactivated carbons with pore-size distributions that are not achievablewith other methods and precursors. Such particulate carbon is availableas P2-15 from EnerG2 Technologies, Inc. (100 NE Northlake Way, Seattle,Wash. 98105, USA; a subsidiary of BASF).

In some embodiments, the particulate carbon has a micropore volume fromabout 0.20 ml/g to about 0.35 ml/g at pore sizes of from about 0.3 nm toabout 1 nm. In some embodiments, the particulate carbon has a microporevolume from about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about0.23 ml/g, about 0.24 ml/g, or about 0.25 mug to about 0.26 ml/g, about0.27 ml/g, about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31ml/g, about 0.32 ml/g, about 0.33 ml/g, about 0.34 ml/g, or about 0.35ml/g.

In some embodiments, the particulate carbon has a mesopore volume offrom about 0.5 mug to about 0.8 mug at pore sizes of from about 1 nm toabout 30 nm. In some embodiments, the particulate carbon has a mesoporevolume of from about 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g toabout 0.65 ml/g, about 0.70 ml/g, about 0.75 ml/g, or about 0.8 ml/g.

In certain embodiments, the particulate carbon has a micropore volumegreater than about 0.2 ml/g, and a mesopore volume greater than about0.5 ml/g. In certain specific embodiments, the particulate carbon has amicropore volume of about 0.3 ml/g and a mesopore volume of about 0.75ml/g. In certain specific embodiments, the particulate carbon has a BETsurface area of about 1400 m²/g, a micropore volume of about 0.3 ml/g,and a mesopore volume of about 0.75 ml/g.

In some embodiments, the particulate carbon has a BET surface area of atleast about 1300 m²/g. In some embodiments, the particulate carbon has aBET surface area of from about 1300 m²/g to about 2100 m²/g. In someembodiments, the particulate carbon has a BET surface area of from about1400 m²/g to about 1600 m²/g. As used herein, the term “BET surfacearea” has its usual meaning of referring to the Brunauer, Emmett, Tellermethod for determining surface area by N₂ adsorption. Pore diameter andpore volume can also be determined using BET-type N₂ adsorption ordesorption experiments.

In some embodiments, the particulate carbon has an n-butane adsorptioncapacity of at least about 40 ml/g at about 3 mm Hg n-butane pressure.In some embodiments, the particulate carbon has an n-butane adsorptioncapacity of from about 40 mug to about 80 mug at about 3 mm Hg n-butanepressure. In some embodiments, the particulate carbon has an n-butaneadsorption capacity of from about 40 ml/g, about 45 ml/g, about 50 ml/g,about 55 ml/g, about 60 ml/g, or about 65 ml/g to about 70 ml/g, about75 ml/g, or about 80 mug at about 3 mm Hg n-butane pressure.

In some embodiments, the particulate carbon may be defined by its ButaneAffinity. The “Butane Affinity” of a material can be calculated bycollecting a butane isotherm measurement as described herein. The butaneisotherm measurement provides a curve plotting the amount of butaneadsorbed vs. the absolute pressure of butane in units of mm Hg. TheButane Affinity can then be calculated by setting the absolute partialpressure of butane at 760 mg Hg (i.e., atmospheric pressure) equal to a“Butane Percentage” of 100% and then plotting the adsorbed amount ofbutane vs. butane percentage. The data curve may be normalized byplotting the amount of butane adsorbed as a fraction of the amount ofbutane adsorbed at a Butane Percentage of 50%. The Butane Affinity at0.5% butane and at 5% butane may then be determined from this plot byreading the fraction of butane adsorbed at 50% at these butaneconcentrations. In other words, the Butane Affinity of the material at5% and 0.5% is the percentage of the butane that the material adsorbs atbutane partial pressures of 38 mm Hg and 3.8 mm Hg, respectfully,compared to the amount of butane that the material adsorbs at 380 mm Hgbutane pressure as determined by the butane isotherm measurement.

In some embodiments, the particulate carbon has a Butane Affinity ofgreater than 60% at 5% butane, for example, from about 60% to about100%, from about 60% to about 99%, from about 65% to about 95%, fromabout 70% to about 90%, or from about 75% to about 85% at 5% butane. Insome embodiments, the particulate carbon has a Butane Affinity of fromabout 75% to about 80% at 5% butane. In some embodiments, theparticulate carbon has a Butane Affinity of greater than 35% at 0.5%butane, for example, from about 35% to about 100%, from about 35% toabout 99%, from about 40% to about 75%, from about 45% to about 60%, orfrom about 45% to about 50% at 0.5% butane. In some embodiments, theparticulate carbon has a Butane Affinity of greater than 60% at 5%butane and a Butane Affinity of greater than 35% at 0.5% butane.

In some embodiments, the particulate carbon has a BET surface area of atleast about 1300 m²/g and a Butane Affinity of greater than 60% at 5%butane. In some embodiments, the particulate carbon has a BET surfacearea of at least about 1300 m²/g and a Butane Affinity of greater than35% at 0.5% butane. In some embodiments, the particulate carbon has aBET surface area of at least about 1300 m²/g, a Butane Affinity ofgreater than 60% at 5% butane, and a Butane Affinity of greater than 35%at 0.5% butane

In some embodiments, the particulate carbon has a BET surface area of atleast about 1300 m²/g; a Butane Affinity of greater than 60% at 5%butane, a Butane Affinity of greater than 35% at 0.5% butane, or both;and a micropore volume greater than about 0.2 ml/g, a mesopore volumegreater than about 0.5 ml/g, or both. In some embodiments, theparticulate carbon has a BET surface area of at least about 1300 m²/g; aButane Affinity of greater than 60% at 5% butane; a Butane Affinity ofgreater than 35% at 0.5% butane; a micropore volume greater than about0.2 ml/g; and a mesopore volume greater than about 0.5 ml/g.Accordingly, any possible combination of these features is contemplated,provided that at least one of said features is present.

The hydrocarbon adsorbent coating further comprises an organic binderthat will cause the adsorbent coating to adhere to the substrate. Uponapplication of the coating as a slurry and drying, the binder materialfixes the hydrocarbon adsorbent particles to themselves and thesubstrate. In some cases, the binder can crosslink with itself toprovide improved adhesion. This enhances the integrity of the coating,its adhesion to the substrate, and provides structural stability undervibrational conditions encountered in motor vehicles. The binder mayalso comprise additives to improve water resistance and improveadhesion. Binders typical for use in the formulation of slurriesinclude, but are not restricted to, the following: organic polymers;sols of alumina, silica or zirconia; inorganic salts, organic saltsand/or hydrolysis products of aluminum, silica or zirconium; hydroxidesof aluminum, silica or zirconium; organic silicates that arehydrolyzable to silica; and mixtures thereof. The preferred binder is anorganic polymer. The organic polymer may be a thermosetting orthermoplastic polymer and may be plastic or elastomeric. The binder maybe, for example, an acrylic/styrene copolymer latex, a styrene-butadienecopolymer latex, a polyurethane, or any mixture thereof. The polymericbinder may contain suitable stabilizers and age resistors known in thepolymeric art. In some embodiments, the binder is a thermosetting,elastomeric polymer introduced as a latex into the adsorbentcomposition, optionally as an aqueous slurry. Preferred arethermosetting, elastomeric polymers introduced as a latex into theadsorbent composition, preferably as an aqueous slurry.

Useful organic polymer binder compositions include polyethylene,polypropylene, polyolefin copolymers, polyisoprene, polybutadiene,polybutadiene copolymers, chlorinated rubber, nitrile rubber,polychloroprene, ethylene-propylene-diene elastomers, polystyrene,polyacrylate, polymethacrylate, polyacrylonitrile, poly(vinyl esters),poly(vinyl halides), polyamides, cellulosic polymers, polyimides,acrylics, vinyl acrylics and styrene acrylics, polyvinyl alcohol,thermoplastic polyesters, thermosetting polyesters, poly (phenyleneoxide), poly(phenylene sulfide), fluorinated polymers such aspoly(tetrafluoroethylene), polyvinylidene fluoride, poly(vinylfluoride)and chloro/fluoro copolymers such as ethylene chlorotrifluoro-ethylenecopolymer, polyamide, phenolic resins and epoxy resins, polyurethane,acrylic/styrene acrylic copolymer latex and silicone polymers. In someembodiment, the polymeric binder is an acrylic/styrene acrylic copolymerlatex, such as a hydrophobic styrene-acrylic emulsion. In someembodiments, the binder is selected from the group consisting of anacrylic/styrene copolymer latex, a styrene-butadiene copolymer latex, apolyurethane, and mixtures thereof.

Considerations regarding the compatibility of the components of a slurrycomprising a hydrocarbon adsorbent material and a polymeric binder, suchas a latex emulsion, are known in the art. See, for instance,commonly-assigned U.S. Publication No. 2007/0107701. In someembodiments, the organic binder can have a low glass transitiontemperature (Tg). Tg is conventionally measured by differential scanningcalorimetry (DSC) by methods known in the art. An exemplary hydrophobicstyrene-acrylic emulsion binder having a low Tg is Rhoplex™ P-376(Trademark of Dow Chemical; available from Rohm and Haas, IndependenceMall West, Philadelphia. Pa., 19105). In some embodiments, the binderhas a Tg less than about 0° C. An exemplary binder having a Tg less thanabout 0° C. is Rhoplex™ NW-1715K (Trademark of Dow Chemical; alsoavailable from Rohm and Haas). In some embodiments, the binder is analkyl phenol ethoxylate (APEO)-free, ultra-low formaldehyde, styrenatedacrylic emulsion. One such exemplary binder is Joncryl™ 2570. In someembodiments, the binder is an aliphatic polyurethane dispersion. Onesuch exemplary binder is Joncryl™ FLX 5200. Joncryl™ is a Trademark ofBASF; Joncryl™ products are available from BASF; Wyandotte, Mich.,48192. In some embodiments, the binder is present in an amount fromabout 10% to about 50% by weight relative to the particulate carbon.

The hydrocarbon adsorbent coatings of the present invention,particularly those slurries containing polymer latexes, can containconventional additives such as thickeners, dispersants, surfactants,biocides, antioxidants and the like. A thickener makes it possible toachieve a sufficient amount of coating (and hence sufficient hydrocarbonadsorption capacity) on relatively low surface area substrates. Thethickener may also serve in a secondary role by increasing slurrystability by steric hindrance of the dispersed particles. It may alsoaid in the binding of the coating surface. Exemplary thickeners are axanthan gum thickener or a carboxymethyl-cellulose thickener. Kelzan®CC, a product of CP Kelco (Cumberland Center II, 3100 CumberlandBoulevard, Suite 600, Atlanta Ga., 30339), is one such exemplary xanthanthickener.

In some embodiments, it is preferred to use a dispersant in conjunctionwith the binder. The dispersant may be anionic, non-ionic or cationicand is typically utilized in an amount of about 0.1 to about 10 weightpercent, based on the weight of the material. Not surprisingly, thespecific choice of dispersant is important. Suitable dispersants mayinclude polyacrylates, alkoxylates, carboxylates, phosphate esters,sulfonates, taurates, sulfosuccinates, stearates, laureates, amines,amides, imidazolines, sodium dodecylbenzene sulfonate, sodium dioctylsulfosuccinate, and mixtures thereof. In one embodiment, the dispersantis a low molecular weight polyacrylic acid in which many of the protonson the acid are replaced with sodium. In some embodiments, thedispersant is a polycarboxylate ammonium salt. In some embodiments, thedispersant is a hydrophobic copolymer pigment dispersant. An exemplarydispersant is Tamol™ 165A (Trademark of Dow Chemical; available fromRohm & Haas). While increasing the slurry pH or adding anionicdispersant alone may provide enough stabilization for the slurrymixture, best results may be obtained when both an increased pH andanionic dispersant are used. In some embodiments, the dispersant is anon-ionic surfactant such as Surfynol® 420 (Air Products and Chemicals,Inc). In some embodiments, the dispersant is an acrylic block copolymersuch as Dispex® Ultra PX 4575 (BASF).

In some embodiments, it is preferred to use a surfactant, which can actas a defoamer. In some embodiments, the surfactant is a low molecularnon-anionic dispersant. An exemplary oil-free and silicone-free defoamersurfactant is Rhodoline® 999 (Solvay). Another exemplary surfactant is ablend of hydrocarbons and non-ionic surfactants, such as Foammaster® NXZ(BASF).

In some embodiments the binder is present in an amount from about 10% toabout 50% by weight relative to the particulate carbon. In someembodiments, the binder is an organic polymer. In some embodiments, thebinder is an acrylic/styrene copolymer latex.

Substrates

In one or more embodiments, the present coating compositions aredisposed on a substrate. Articles comprising the coated substrates, suchas a bleed emission scrubber may, in some embodiments, be part of anevaporative emission control systems. Present substrates are3-dimensional, having a length and a diameter and a volume, similar to acylinder. The shape does not necessarily have to conform to a cylinder.The length is an axial length defined by an inlet end and an outlet end.The diameter is the largest cross-section length, for example thelargest cross-section if the shape does not conform exactly to acylinder. In one or more embodiments, the substrate is monolith,described herein below.

As used herein, the term “monolithic substrate” is a substrate of thetype having fine, parallel gas flow passages extending there throughfrom an inlet or an outlet face of the substrate such that passages areopen to fluid flow there through. The passages, which may be essentiallystraight paths or may be patterned paths (e.g., zig-zag, herringbone,etc.) from their fluid inlet to their fluid outlet, are defined by wallson which the adsorbent material is coated as a washcoat so that thegases flowing through the passages contact the adsorbent material. Theflow passages of the monolithic substrate are thin-walled channels,which can be of any suitable cross-sectional shape and size such astrapezoidal, rectangular, square, triangular, sinusoidal, hexagonal,oval, circular, etc. Such structures may contain from about 60 to about900 or more gas inlet openings (i.e., cells) per square inch of crosssection. Monolithic substrates may be comprised of, for example, metal,ceramic, plastic, paper, impregnated paper, and the like. In someembodiments, the substrate is a carbon monolith.

In one or more embodiments, the substrate is selected from the groupconsisting of foams, monolithic materials, non-wovens, wovens, sheets,papers, twisted spirals, ribbons, structured media of extruded form,structured media of wound form, structured media of folded form,structured media of pleated form, structured media of corrugated form,structured media of poured form, structured media of bonded form, andcombinations thereof.

In one embodiment, the substrate is an extruded media. In someembodiments, the extruded media is a honeycomb. The honeycomb may be inany geometrical shape including, but not limited to, round, cylindrical,or square. Furthermore, the cells of honeycomb substrates may be of anygeometry.

In one embodiment, the substrate is a foam. In some embodiments, thefoam has greater than about 10 pores per inch. In some embodiments, thefoam has greater than about 20 pores per inch. In some embodiments, thefoam has between about 15 and about 40 pores per inch. In someembodiments, the foam is a polyurethane. In some embodiments, the foamis a reticulated polyurethane. In some embodiments, the polyurethane isa polyether or polyester. In some embodiments, the substrate is anon-woven.

In some embodiments, the substrate is a plastic. In some embodiments,the substrate is a thermoplastic polyolefin. In some embodiments, thesubstrate is a thermoplastic polyolefin containing a glass or mineralfiller. In some embodiments, the substrate is a plastic selected fromthe group consisting of polypropylene, nylon-6, nylon-6,6, aromaticnylon, polysulfone, polyether sulfone, polybutylene terephthalate,polyphthalamide, polyoxymethylene, polycarbonate, polyvinylchloride,polyester, and polyurethane.

In certain alternative embodiments, the particulate carbon may becombined with additional materials and extruded to form an adsorptiveporous monolith. Accordingly, such porous monoliths represent adsorbentarticles which do not include a substrate and adsorbent coating, and maybe utilized in, for example, a bleed emission scrubber as describedherein below. To prepare such porous monoliths, generally, theparticulate carbon as described herein may be combined with, forexample, a ceramic forming material, flux material, binder, and water tomake an extrudable mixture. The extrudable mixture may then be extrudedthrough an extrusion die to form a monolith having a honeycombstructure. After extrusion, the extruded honeycomb monolith may be driedand then fired at a temperature and for a time period sufficient to forma monolith having the particulate carbon dispersed throughout thestructure. Suitable methods for preparing such extruded porous monolithsare disclosed in, for example, U.S. Pat. No. 5,914,294 to Park et al.,the disclosure of which is incorporated by reference herein with respectto such methods.

Articles—Bleed Emission Scrubber

In one aspect of the disclosure is provided a bleed emission scrubber,the scrubber comprising an adsorbent volume comprising a coatedsubstrate as described herein, adapted for hydrocarbon adsorption, thecoated substrate comprising at least one surface, and a coating on theat least one surface, the coating comprising particulate carbon asdescribed herein and a binder as described herein, wherein theparticulate carbon has a BET surface area of at least about 1300 m²/g;and at least one of: (i) a butane affinity of greater than 60% at 5%butane; (ii) a butane affinity of greater than 35% at 0.5% butane; (iii)a micropore volume greater than about 0.2 ml/g and a mesopore volumegreater than about 0.5 ml/g. In some embodiments, the particulate carbonhas an n-butane adsorption capacity of at least about 40 ml/g at about 3mm Hg n-butane pressure. In some embodiments, the particulate carbon hasan n-butane adsorption capacity of from about 40 ml/g to about 80 ml/gat about 3 mm Hg n-butane pressure. In some embodiments, the particulatecarbon has an n-butane adsorption capacity of from about 40 ml/g, about45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/gto about 70 ml/g, about 75 ml/g, or about 80 ml/g at about 3 mm Hgn-butane pressure.

In some embodiments, the particulate carbon has a BET surface area offrom about 1300 m²/g to about 2500 m²/g. In some embodiments, theparticulate carbon has a BET surface area of from about 1400 m²/g toabout 1600 m²/g.

In some embodiments, the particulate carbon has a micropore volume isfrom about 0.20 ml/g to about 0.35 ml/g. In some embodiments, theparticulate carbon has a micropore volume is from about 0.20 ml/g, about0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0.32 ml/g, about 0.33ml/g, about 0.34 ml/g, or about 0.35 ml/g.

In some embodiments, the particulate carbon has a mesopore volume offrom about 0.5 ml/g to about 0.8 ml/g. In some embodiments, theparticulate carbon has a mesopore volume of from about 0.5 ml/g, about0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about0.75 ml/g, or about 0.8 ml/g.

In some embodiments, the particulate carbon has a BET surface area ofabout 1400 m²/g, a micropore volume of about 0.3 ml/g, and a mesoporevolume of about 0.75 ml/g.

In some embodiments, the adsorbent volume has a g-total butane workingcapacity (BWC) of less than about 2 grams. As used herein, “g-total BWC”refers to the amount of butane purged under standard test conditions(e.g., ASTM D5228). In some embodiments, the adsorbent volume has ag-total BWC of from about 0.2 grams to about 1.6 grams. for example,from about 0.2 grams, about 0.3 grams, about 0.4 grams, about 0.5 grams,about 0.6 grams, about 0.7 grams, about 0.8 grams, about 0.9 grams, orabout 1 gram, to about 1.1 grams, about 1.2 grams, about 1.3 grams,about 1.4 grams, about 1.5 grams, or about 1.6 grams.

In some embodiments, the adsorbent volume has an effective butaneworking capacity (BWC) of less than 3 g/dL. As used herein, “effectivebutane working capacity” refers to g-total BWC divided by the effectiveadsorbent volume. Effective adsorbent volume corrects for voids, airgaps, and other non-adsorptive volumes. Effective BWC determination isdisclosed in, for example, U.S. Patent Application Publication No.2015/0275727, which is incorporated by reference herein.

FIG. 1A illustrates an embodiment of bleed emission scrubber 1, whereinthe coated substrate is a structured media of pleated form (2 a). FIG.1B illustrates an embodiment wherein the coated substrate is a foam 2 b.In one embodiment, the foam 2 b has greater than about 10 pores perinch. In some embodiments, the foam 2 b has greater than about 20 poresper inch. In some embodiments, the foam 2 b has between about 15 andabout 40 pores per inch. In one embodiment, the foam 2 b is apolyurethane. In some embodiments, the foam 2 b is a reticulatedpolyurethane. In some embodiments, the polyurethane is a polyether orpolyester.

FIG. 1C illustrates an embodiment wherein the coated substrate is anextruded media 2 c. In some embodiments, the extruded media 2 c is ahoneycomb. The honeycomb adsorbent may be in any geometrical shapeincluding, but not limited to, round, cylindrical, or square.Furthermore, the cells of honeycomb adsorbents may be of any geometry.Honeycombs of uniform cross-sectional areas for the flow-throughpassages, such as square honeycombs with square cross-sectional cells orspiral wound honeycombs of corrugated form, may perform better thanround honeycombs with square cross-sectional cells in a right angledmatrix that provides adjacent passages with a range of cross-sectionalareas and therefore passages that are not equivalently purged. Withoutbeing bound by any theory, it is believed that the more uniform cellcross-sectional areas across the honeycomb faces, the more uniform flowdistribution within the scrubber during both adsorption and purgecycles, and, therefore, lower diurnal breathing loss (DBL) emissionsfrom the scrubber.

Surprisingly, it has been found that the adsorbent volume of bleedemission scrubbers as disclosed herein, can, in some embodiments, have abutane working capacity (BWC) lower than that of competitive monoliths,yet still effectively control the hydrocarbon emissions from anevaporative emission control canister under low purge conditions.

Particularly, foam substrates as disclosed herein exhibit a lower butaneworking capacity than competitive monoliths, yet more efficientlycontrol emissions under low purge volumes. Without wishing to be boundby theory, this may be due to the low thickness of the adsorbentcoating, and/or the high turbulence of the gas flow though the foam,which may provide more rapid purging than the bulk monolith used incompetitive products.

In certain embodiments, the adsorbent volume does not comprise a coatedsubstrate, instead comprising a porous extruded monolith comprising theparticulate carbon as described herein.

Evaporative Emission Control Canister and Canister Systems

The coated substrate for hydrocarbon adsorption as disclosed herein canbe used as a component in an evaporative emission control canistersystem. Therefore, in yet another aspect an evaporative emission controlcanister system comprising an evaporative emission control canistercomprising at least one canister adsorbent volume comprising a canisteradsorbent material, and at least one bleed emission scrubber asdisclosed herein; wherein the at least one bleed emission scrubbercomprises a scrubber adsorbent volume, wherein the scrubber adsorbentvolume comprises a scrubber adsorbent material and has a g-total BWC ofless than about 2 grams; wherein the bleed emission scrubber is in fluidcommunication with the evaporative emission control canister; whereinthe evaporative emission control canister is configured to permitsequential contact of the canister adsorbent volume and the scrubberadsorbent volume by the fuel vapor; and wherein the evaporative emissioncontrol canister has a 2-Day Diurnal Breathing Loss (DBL) of less thanabout 20 mg under the California Bleed Emission Test Protocol (BETP). Insome embodiments, the evaporative emission control canister system has a2-Day Diurnal Breathing Loss (DBL) of less than about 20 mg under theCalifornia Bleed Emission Test Protocol (BETP) when tested under thefollowing test conditions: a total canister adsorbent material volume inthe evaporative emission control canister of 2.5 L and a purge volume of80 bed volumes. In some embodiments, the evaporative emission controlcanister system has a 2-Day Diurnal Breathing Loss (DBL) of less thanabout 20 mg under the California Bleed Emission Test Protocol (BETP)when tested under the following test conditions: a total canisteradsorbent material volume in the evaporative emission control canisterof 1.9 L and a purge volume of 135 bed volumes.

In some embodiments, the evaporative emission control canister furthercomprises a fuel vapor purge tube for connecting the evaporativeemission control canister to an engine, a fuel vapor inlet conduit forventing the fuel tank to the evaporative emission control canister, anda vent conduit for venting the evaporative emission control canister tothe atmosphere and for admission of purge air to the evaporativeemission control canister.

In some embodiments, the canister adsorbent material is selected fromthe group consisting of activated carbon, carbon charcoal, zeolites,clays, porous polymers, porous alumina, porous silica, molecular sieves,kaolin, titania, ceria, and combinations thereof. In some embodiments,the activated carbon is derived from a material including a memberselected from the group consisting of wood, wood dust, wood flour,cotton linters, peat, coal, coconut, lignite, carbohydrates, petroleumpitch, petroleum coke, coal tar pitch, fruit pits, fruit stones, nutshells, nut pits, sawdust, palm, vegetables, synthetic polymer, naturalpolymer, lignocellulosic material, and combinations thereof.

In some embodiments, the scrubber adsorbent material comprises aparticulate carbon, wherein the particulate carbon has a BET surfacearea of at least about 1300 m²/g; and at least one of: (i) a butaneaffinity of greater than 60% at 5% butane; (ii) a butane affinity ofgreater than 35% at 0.5% butane; (iii) a micropore volume greater thanabout 0.2 ml/g and a mesopore volume greater than about 0.5 ml/g.

In some embodiments, the particulate carbon has an n-butane adsorptioncapacity of at least about 40 ml/g at about 3 mm Hg n-butane pressure.In some embodiments, the particulate carbon has an n-butane adsorptioncapacity of from about 40 ml/g to about 80 ml/g at about 3 mm Hgn-butane pressure. In some embodiments, the particulate carbon has ann-butane adsorption capacity of from about 40 ml/g, about 45 ml/g, about50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g to about 70ml/g, about 75 ml/g, or about 80 mug at about 3 mm Hg n-butane pressure.

In some embodiments, the particulate carbon has a BET surface area offrom about 1300 m²/g to about 2500 m²/g. In some embodiments, theparticulate carbon has a BET surface area of from about 1400 m²/g toabout 1600 m²/g.

In some embodiments, the particulate carbon has a micropore volume offrom about 0.20 mug to about 0.35 ml/g. In some embodiments, theparticulate carbon has a micropore volume of from about 0.20 ml/g, about0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0.32 ml/g, about 0.33ml/g, about 0.34 ml/g, or about 0.35 ml/g.

In some embodiments, the particulate carbon has a mesopore volume offrom about 0.5 mug to about 0.8 ml/g. In some embodiments, theparticulate carbon has a mesopore volume of from about 0.5 ml/g, about0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about0.75 ml/g, or about 0.8 ml/g.

In some embodiments, the particulate carbon has a BET surface area ofabout 1400 m²/gram, a micropore volume of about 0.3 ml/g, and a mesoporevolume of about 0.75 ml/g.

In some embodiments, the bleed emissions scrubber comprises a substrate.In some embodiments, the substrate is selected from the group consistingof foams, monolithic materials, non-wovens, wovens, sheets, papers,twisted spirals, ribbons, structured media of extruded form, structuredmedia of wound form structured media of folded form, structured media ofpleated form, structured media of corrugated form, structured media ofpoured form, structured media of bonded form, and combinations thereof.In some embodiments, the substrate is molded, formed or extruded with amixture comprising the scrubber adsorbent material. In some embodiments,the substrate comprises a coating, wherein the coating comprises thescrubber adsorbent material and a binder. In some embodiments, thesubstrate is a monolith. In some embodiments, the monolith is a ceramic.In some embodiments, the substrate is a plastic. In some embodiments,the plastic is selected from the group consisting of polypropylene,nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyether sulfone,polybutylene terephthalate, polyphthalamide, polyoxymethylene,polycarbonate, polyvinylchloride, polyester, and polyurethane.

In some embodiments, the coating thickness is less than about 500microns.

In some embodiments, the binder is present in an amount from about 10%to about 50% by weight relative to the particulate carbon. In someembodiments, the binder is an organic polymer. In some embodiments, thebinder is an acrylic/styrene copolymer latex.

In some embodiments, the second adsorbent volume has an effective BWC ofless than about 2 grams/dl. In some embodiments, the second adsorbentvolume has an effective BWC of from about 0.5 grams/dl to about 2grams/dl. In some embodiments, the second adsorbent volume has aneffective BWC of from about 0.5, about 0.6, about 0.7, about 0.8, orabout 0.9 to about 1.0, about 1.1, about 1.2, about 1.3, about 1.4,about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, or about 2.0grams/dL. In some embodiments, the second adsorbent volume has a g-totalBWC from about 0.1 grams to less than about 2 grams. In someembodiments, the second adsorbent volume has a g-total BWC of from about0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7,about 0.8, or about 0.9, to about 1.0, about 1.1, about 1.2, about 1.3,about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, or about 1.9grams.

In some embodiments, the evaporative emission control canister has acanister adsorbent volume of 3.5 L or less, 3.0 L or less, 2.5 L orless, or 2.0 L or less.

In some embodiments, the evaporative emission control canister systemcomprises a single canister adsorbent volume, wherein the canisteradsorbent volume comprises at least one chamber, wherein there iscanister adsorbent material loaded within the at least one chamber; asingle bleed emission scrubber, wherein the at least one bleed emissionscrubber comprises a scrubber adsorbent volume, wherein the scrubberadsorbent volume comprises a scrubber adsorbent material and has ag-total BWC of less than about 2 grams; a canister adsorbent volume offrom about 1.5 L to about 2.0 L; wherein the evaporative emissioncontrol canister system has a 2-Day Diurnal Breathing Loss (DBL) of lessthan about 20 mg under the California Bleed Emission Test Protocol(BETP) at a purge volume of 135 bed volumes. In some embodiments, theevaporative emission control canister has a 2-Day Diurnal Breathing Loss(DBL) of less than about 10 mg under the California Bleed Emission TestProtocol (BETP).

In some embodiments, the canister adsorbent volume comprises twochambers, wherein there is canister adsorbent material loaded withineach chamber. In some embodiments, the second adsorbent volume has aneffective BWC of less than about 2 grams/dl. In some embodiments, thesecond adsorbent volume has an effective BWC of from about 0.5 grams/dlto about 2 grams/dl. In some embodiments, the second adsorbent volumehas an effective BWC of from about 0.5, about 0.6, about 0.7, about 0.8,or about 0.9 to about 1.0, about 1.1, about 1.2, about 1.3, about 1.4,about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, or about 2.0grams/dL. In some embodiments, the second adsorbent volume has a g-totalBWC from about 0.1 grams to less than about 2 grams. In someembodiments, the second adsorbent volume has a g-total BWC of from about0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7,about 0.8, or about 0.9, to about 1.0, about 1.1, about 1.2, about 1.3,about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, or about 1.9grams.

In some embodiments, the evaporative emission control canister comprisesa single canister adsorbent volume, wherein the canister adsorbentvolume comprises at least one chamber, wherein there is canisteradsorbent material loaded within the at least one chamber; a singlebleed emission scrubber; a canister volume of from about 2.5 L to about3.0 L; wherein the evaporative emission control canister has a 2-DayDiurnal Breathing Loss (DBL) of less than about 20 mg under theCalifornia Bleed Emission Test Protocol (BETP) at a purge volume of 80bed volumes. In some embodiments, the evaporative emission controlcanister has a 2-Day Diurnal Breathing Loss (DBL) of less than about 10mg under the California Bleed Emission Test Protocol (BETP).

In some embodiments, the canister adsorbent volume comprises twochambers, wherein there is canister adsorbent material loaded withineach chamber. In some embodiments, the second adsorbent volume has aneffective BWC of less than about 2 grams/dl. In some embodiments, thesecond adsorbent volume has an effective BWC of from about 0.5 grams/dlto about 2 grams/dl. In some embodiments, the second adsorbent volumehas an effective BWC of from about 0.5, about 0.6, about 0.7, about 0.8,or about 0.9 to about 1.0, about 1.1, about 1.2, about 1.3, about 1.4,about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, or about 2.0grams/dL. In some embodiments, the second adsorbent volume has a g-totalBWC from about 0.1 grams to less than about 2 grams. In someembodiments, the second adsorbent volume has a g-total BWC of from about0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7,about 0.8, or about 0.9, to about 1.0, about 1.1, about 1.2, about 1.3,about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, or about 1.9grams.

Evaporative Emission Control System

The evaporative emission control canister system as disclosed herein canbe used as a component in an evaporative emission control system forfuel storage. Therefore, in yet another aspect is provided anevaporative emission control system, the evaporative emission controlsystem comprising a first adsorbent volume contained within a firstcanister, a fuel vapor purge tube for connecting the first canister toan engine, a fuel vapor inlet conduit for venting the fuel tank to thefirst canister, and a vent conduit for venting the first canister to theatmosphere and for admission of purge air to the first canister; and asecond adsorbent volume comprising the bleed emission scrubber asdisclosed herein; wherein the second adsorbent volume is in fluidcommunication with the first adsorbent volume, the bleed emissionscrubber being contained within the first canister or contained within asecond canister; and wherein the evaporative emission control system isconfigured to permit sequential contact of the first adsorbent volumeand the second adsorbent volume by the fuel vapor. In some embodiments,the evaporative emission control system further comprises a fuel tankfor fuel storage; and an internal combustion engine adapted to consumethe fuel; wherein the evaporative emission control system is defined bya fuel vapor flow path from the fuel vapor inlet conduit to the firstcanister, toward the second adsorbent volume and to the vent conduit,and by a reciprocal air flow path from the vent conduit to the secondadsorbent volume, toward the first canister, and toward the fuel vaporpurge tube.

Evaporative emissions from the fuel tank are adsorbed by the evaporativeemission control system during engine off times. The fuel vapor thatbleeds from the fuel tank is removed by the adsorbents in the canistersystem so that the amount of fuel vapor released into the atmosphere isreduced. At the time of operating the engine, atmospheric air isintroduced into the canister system and bleed emission scrubber as apurge stream, whereby the hydrocarbons, which were previously adsorbedby the hydrocarbon adsorbent, are desorbed and recirculated to theengine for combustion through a purge line.

The evaporative emission control canister of the evaporative emissioncontrol system typically comprises a three-dimensional hollow interiorspace or chamber defined at least in part by a shaped planar material,such as molded thermoplastic olefin. In some embodiments, the bleedemission scrubber is located within the first adsorbent volume of theevaporative emission control canister. In some embodiments, the bleedemission scrubber is located in a separate canister that is in fluidcommunication with the evaporative emission control canister. Theevaporative emission control system of the present invention accordingto the embodiment wherein the bleed emission scrubber is located in aseparate canister may be more readily appreciated by reference to FIG. 2. FIG. 2 schematically illustrates an evaporative emission controlsystem 30 according to one embodiment of the invention. The evaporativeemission control system 30 comprises a fuel tank 38 for fuel storage, aninternal combustion engine 32 adapted to consume the fuel, anevaporative emission control canister 46 and a bleed emission scrubber1. The engine 32 is preferably an internal combustion engine that iscontrolled by a controller 34. The engine 32 typically burns gasoline,ethanol and other volatile hydrocarbon-based fuels. The controller 34may be a separate controller or may form part of an engine controlmodule (ECM), a powertrain control module (PCM) or any other vehiclecontroller.

In accordance with an embodiment of the invention, the evaporativeemission control canister 46 comprises a first adsorbent volume(represented by 48), a fuel vapor purge tube 66 connecting theevaporative emission control canister 46 to the engine 32, a fuel vaporinlet conduit 42 for venting the fuel tank 38 to the evaporativeemission control canister 46, and vent conduit 56, 59, 60 for ventingthe evaporative emission control canister 46 to the atmosphere and foradmission of purge air to the evaporative emission control canistersystem.

The evaporative emission control canister system is further defined by afuel vapor flow path from the fuel vapor inlet conduit 42 to the firstadsorbent volume 48, through vent conduit 56 toward the bleed emissionscrubber 1 and to the vent conduit 59, 60, and by a reciprocal air flowpath from the vent conduit 60, 59 to the bleed emission scrubber 58,through vent conduit 56 toward the first adsorbent volume 48, and towardthe fuel vapor purge tube 66. The bleed emission scrubber 1 comprises atleast a second adsorbent volume, the second adsorbent volume comprisinga coated substrate 2 adapted for hydrocarbon adsorption, as provided anddescribed herein.

Fuel vapor, containing hydrocarbons which have evaporated from the fueltank 38, can pass from the fuel tank 38 to the first adsorbent volume 48within canister 46 through evaporative vapor inlet conduit 42. Theevaporative emission control canister 46 may be formed from any suitablematerial. For example, molded thermoplastic polymers such as nylon aretypically used.

Fuel vapor pressure increases as the temperature of the gasoline in fueltank 38 increases. Without the evaporative emission control system 30 ofthe present invention, the fuel vapor would be released to theatmosphere untreated. However, in accordance with the present invention,fuel vapors are treated by evaporative emission control canister 46 andby the bleed emission scrubber 1, located downstream of the evaporativeemission control canister 46.

When the vent valve 62 is open, and purge valve 68 closed, fuel vaporsflow under pressure from the fuel tank 38 through the evaporative vaporinlet conduit 42, the canister vapor inlet 50 and sequentially throughthe first adsorbent volume 48 contained within the evaporative emissioncontrol canister 46. Subsequently, any fuel vapors not adsorbed by thefirst adsorbent volume flow out of the evaporative emission controlcanister 46 via vent conduit opening 54 and vent conduit 56. The fuelvapors then enter bleed emission scrubber 1 for further adsorption.After passage through the bleed emission scrubber 1, any remaining fuelvapors exit the bleed emission scrubber 1 via conduit 59, vent valve 62,and the vent conduit 60, thereby being released to the atmosphere.

Gradually, the hydrocarbon adsorbent material contained in both theevaporative emission control canister 46 and the second adsorbent volumeof bleed emission scrubber 1 become laden with hydrocarbons adsorbedfrom the fuel vapor. When hydrocarbon adsorbents become saturated withfuel vapor, and thus, hydrocarbons, the hydrocarbons must be desorbedfrom the hydrocarbon adsorbents for continued control of emitted fuelvapors from the fuel tank 38. During engine operation, engine controller34 commands valves 62 and 68, via signal leads 64 and 70, respectively,to open, thereby creating an air flow pathway between the atmosphere andthe engine 32. The opening of the purge valve 68 allows clean air to bedrawn into bleed emission scrubber 1 and subsequently into theevaporative emission control canister 46 via the vent conduit 60, ventconduit 59 and vent conduit 56, from the atmosphere. The clean air, orpurge air, flows in through the clean air vent conduit 60, through bleedemission scrubber 1, through vent conduit 56, through the vent conduitopening 54 and into evaporative emission control canister 46. The cleanair flows past and/or through the hydrocarbon adsorbents containedwithin bleed emission scrubber 1 and the emission control canister 46,desorbing hydrocarbons from the saturated hydrocarbon adsorbents withineach volume. A stream of purge air and hydrocarbons then exitsevaporative emission control canister 46 through purge opening outlet52, purge line 66 and purge valve 68. The purge air and hydrocarbonsflow through purge line 72 to the engine 32, where the hydrocarbons aresubsequently combusted.

In some embodiments, the particulate carbon has an n-butane adsorptioncapacity of at least about 40 ml/g at about 3 mm Hg n-butane pressure.In some embodiments, the particulate carbon has an n-butane adsorptioncapacity of from about 40 ml/g to about 80 ml/g at about 3 mm Hgn-butane pressure. In some embodiments, the particulate carbon has ann-butane adsorption capacity of from about 40 ml/g, about 45 ml/g, about50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g to about 70ml/g, about 75 ml/g, or about 80 ml/g at about 3 mm Hg n-butanepressure. In some embodiments, the particulate carbon has a BET surfacearea of from about 1300 m²/g to about 2500 m²/g. In some embodiments,the particulate carbon has a BET surface area of from about 1400 m²/g toabout 1600 m²/g. In some embodiments, the particulate carbon has amicropore volume of from about 0.20 ml/g to about 0.35 ml/g. In someembodiments, the particulate carbon has a micropore volume of from about0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24ml/g, or about 0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0.32ml/g, about 0.33 ml/g, about 0.34 ml/g, or about 0.35 ml/g. In someembodiments, the particulate carbon has a mesopore volume of from about0.5 ml/g to about 0.8 ml/g. In some embodiments, the particulate carbonhas a mesopore volume of from about 0.5 ml/g, about 0.55 ml/g, or about0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about 0.75 ml/g, or about0.8 ml/g. In some embodiments, the particulate carbon has a BET surfacearea of about 1400 m²/gram, a micropore volume of about 0.3 ml/g, and amesopore volume of about 0.7 ml/g. In some embodiments, the particulatecarbon has a BET surface area of at least about 1300 m²/g; and at leastone of: (i) a butane affinity of greater than 60% at 5% butane; (ii) abutane affinity of greater than 35% at 0.5% butane; (iii) a microporevolume greater than about 0.2 ml/g and a mesopore volume greater thanabout 0.5 ml/g.

In some embodiments, the substrate is selected from the group consistingof foams, monolithic materials, non-wovens, wovens, sheets, papers,twisted spirals, ribbons, structured media of extruded form, structuredmedia of wound form structured media of folded form, structured media ofpleated form, structured media of corrugated form, structured media ofpoured form, structured media of bonded form, and combinations thereof.In some embodiments, the substrate is a monolith. In some embodiments,the monolith is a ceramic. In some embodiments, the substrate is aplastic. In some embodiments, the plastic is selected from the groupconsisting of polypropylene, nylon-6, nylon-6,6, aromatic nylon,polysulfone, polyether sulfone, polybutylene terephthalate,polyphthalamide, polyoxymethylene, polycarbonate, polyvinylchloride,polyester, and polyurethane. In some embodiments, the coating thicknessis less than about 500 microns. In some embodiments, the binder ispresent in an amount from about 10% to about 50% by weight relative tothe particulate carbon. In some embodiments, the binder is an organicpolymer. In some embodiments, the binder is an acrylic/styrene copolymerlatex.

In some embodiments, the bleed emission scrubber is contained in thefirst canister. In some embodiments, the bleed emission scrubber iscontained in the second canister.

In some embodiments, the second adsorbent volume within bleed emissionscrubber 1 has an effective an effective butane working capacity (BWC)of less than about 3 g/dL, and a g-total BWC of less than about 2 grams.In some embodiments, the second adsorbent volume has a g-total BWC offrom about 0.2 grams to about 1.999 grams.

In some embodiments, the second adsorbent volume further comprises athird adsorbent volume, the third adsorbent volume having a BWC of atleast about 0.05 grams. In some embodiments, the third adsorbent volumecomprises a reticulated polyurethane foam. FIG. 3 schematicallyillustrates a bleed emission scrubber 1 wherein the substrate comprisingthe second adsorbent volume is an extruded media 2 a and the thirdadsorbent volume comprises a substrate comprising a reticulatedpolyurethane foam 2 b.

The second adsorbent volume (and any additional adsorbent volumes) mayinclude a volumetric diluent. Non-limiting examples of the volumetricdiluents may include, but are not limited to, spacers, inert gaps,foams, fibers, springs, or combinations thereof. Additionally, theevaporative emission control canister system may include an empty volumeanywhere within the system. As used herein, the term “empty volume”refers to a volume not including any adsorbent. Such volume may compriseany non-adsorbent including, but not limited to, air gap, foam spacer,screen, or combinations thereof.

In some embodiments, the 2-Day Diurnal Breathing Loss (DBL) of theevaporative emission control system is less than about 20 mg under theCalifornia Bleed Emission Test Protocol (BETP).

In some embodiments, the first adsorbent volume is from about 1.9 toabout 3.0 liters, and the 2-Day Diurnal Breathing Loss (DBL) is lessthan about 20 mg under the California Bleed Emission Test Protocol(BETP) when tested under the following test conditions: a total canisteradsorbent material volume in the evaporative emission control canisterof 1.9 L and a purge volume of 135 bed volumes, or a total canisteradsorbent material volume in the evaporative emission control canisterof 2.5 L and a purge volume of 80 bed volumes.

In some embodiments, the evaporative emission control system maintains a2-day DBL that is less than about 20 mg under the California BETP, withthe second absorbent volume having a g-total BWC of less than about 2grams.

It will be readily apparent to one of ordinary skill in the relevantarts that suitable modifications and adaptations to the compositions,methods, and applications described herein can be made without departingfrom the scope of any embodiments or aspects thereof. The compositionsand methods provided are exemplary and are not intended to limit thescope of the claimed embodiments. All of the various embodiments,aspects, and options disclosed herein can be combined in all variations.The scope of the compositions, formulations, methods, and processesdescribed herein include all actual or potential combinations ofembodiments, aspects, options, examples, and preferences herein. Allpatents and publications cited herein are incorporated by referenceherein for the specific teachings thereof as noted, unless otherspecific statements of incorporation are specifically provided.

EXAMPLES

The present invention is more fully illustrated by the followingexamples, which are set forth to illustrate the present invention and isnot to be construed as limiting thereof. Unless otherwise noted, allparts and percentages are by weight, and all weight percentages areexpressed on a dry basis, meaning excluding water content, unlessotherwise indicated.

Example 1: Preparation of Coated Monolith Using Carbon 1

A solution of 1.4% Kelzan CC in water was prepared one day in advance ofuse. Water (310 ml) was combined with 21 ml of the Kelzan CC thickenersolution, 0.65 g of Surfynol 420 dispersant and 0.5 g Foammaster NXZantifoamer and the combination was mixed thoroughly. To this mixture wasadded 100 g of a high surface area activated carbon adsorbent (P2-15from EnerG2 Technologies, Inc; “Carbon 1” of Table 1; inventiveembodiment) with stirring. The resulting carbon dispersion was added toa second vessel containing 40 g of Joncryl 2570 binder (50% solution)with stirring. Additional Kelzan CC thickener solution was added untilthe slurry viscosity was sufficient for coating purposes.

Cylindrical ceramic monolith substrates (230 cells per square inch) of29×100 mm size (width×length) were dipped into the slurry. Excess slurrywas removed by clearing the channels using an air-knife operated at 15psig pressure. The substrate was dried at 110° C. for 2 hr. Theprocedure was repeated until the desired carbon loading was achieved.

The g-total BWC of this sample was determined to be 1.29 g, and itseffective BWC was determined to be 1.95 g n-butane/dL.

Example 2: Preparation of Coated Monolith Using Carbon 2 (Comparative)

A solution of 1.4% Kelzan CC in water was prepared one day in advance ofuse. Water (483 ml) was combined with 84.58 g of the Kelzan CC thickenersolution, 1.33 g of Surfynol 420 dispersant and 1.03 g Foammaster NXZantifoamer and the combination was mixed thoroughly. To this mixture wasadded 205.06 g activated carbon adsorbent (“Carbon 2” of Table 1;comparative) with stirring. The resulting carbon dispersion was added toa second vessel containing 79.93 g of Joncryl 2570 binder (50% solution)with stirring.

Cylindrical ceramic monolith substrates (230 cells per square inch) of29×100 mm size (width×length) were dipped into the slurry. Excess slurrywas removed by clearing the channels using an air-knife operated at 15psig pressure. The substrate was dried at 110° C. for 2 hr. Theprocedure was repeated until the desired carbon loading was achieved.

The g-total BWC of this sample was determined to be 1.28 g and itseffective BWC was determined to be 1.94 g n-butane/dL.

Example 3: Preparation of Coated Monolith Using Carbon 3 (Comparative)

A solution of 1.4% Kelzan CC in water was prepared one day in advance ofuse. Water (475 ml) was combined with 31.4 ml of the Kelzan CC thickenersolution, 0.98 g of Surfynol 420 dispersant and 0.75 g Foammaster NXZantifoamer and the combination was mixed thoroughly. To this mixture wasadded 50 g activated carbon adsorbent (“Carbon 3” of Table 1;comparative) with stirring. To the carbon dispersion was added 92.6 g ofJoncryl FLX5020 binder (50% solution) with stirring. To the slurry wasadded 4.9 g of a 30% ammonium hydroxide solution to adjust the pH to8.5. To the slurry was added 100 g of a second activated carbon (“Carbon1” of Table 1) with stirring. Water was added as needed until the slurryrheology was sufficient for coating purposes.

Cylindrical ceramic monolith substrates (230 cells per square inch) of29×100 mm size (width×length) were dipped into the slurry. Excess slurrywas removed by clearing the channels using an air-knife operated at 15psig pressure. The substrate was dried at 110° C. for 2 hr. Theprocedure was repeated until the desired carbon loading was achieved.

The g-total BWC of this sample was determined to be 1.24 and itseffective BWC was determined to be 1.88 g n-butane/dL.

Comparative Example

An Ingevity bleed emission trap of size 29×100 mm and with 230 cells persquare inch was tested, in addition to Examples 1-3, in the followingtests. The carbon content was determined by LOI up to 1000° C. to be31.8 wt %. The total weight of the monolith was ˜28 g. This carboncontent was used to correct the measured surface area, pore volume, andbutane absorption capacity in the Examples below. The surface area andpore volume characterization of this comparative carbon are provided inTable 1 (Comparative Example).

The g-total BWC of this sample was determined to be 2.21 g and itseffective BWC was determined to be 3.35 g n-butane/L.

Example 4: Measurement of Surface Areas and Pore Size Distributions

Nitrogen pore size distribution and surface area analysis were performedon Micromeritics TriStar 3000 series instruments. The material to betested was degassed for a total of 6 hours (a 2 hour ramp to 300° C.,then a hold at 300° C. for 4 hours, under a flow of dry nitrogen) on aMicromeritics SmartPrep degasser. Nitrogen BET surface area wasdetermined using 5 partial pressure points between 0.08 and 0.20. TheNitrogen pore size was determined using the BJH calculations and 33desorption points (FIGS. 4 and 5 ).

TABLE 1 Comparative surface area and pore volume data. Surface Porevolume [ml/g] Pore volume [ml/g] Absorbent area [m²/g] radius 1-30 nmwidth 0.3-1 nm Carbon 1 1516 0.70 0.291 Carbon 2 1361 0.10 0.285 Carbon3 2009 1.15 0.145 Comparative 1247* 1.00* 0.150* Example *mathematicallydetermined by dividing the surface area or pore volume by the carboncontent

Example 5: Measurement of Butane Isotherms

Butane isotherms were obtained for several adsorbent materials. A butaneisotherm measurement measures the adsorbed amount of butane in a sampleadsorbent material as a function of the partial pressure of butane at aconstant temperature.

The butane isotherms were collected according to the followingprocedure. Butane gas was introduced incrementally into the evacuatedsample, allowed to reach equilibrium and the adsorbed mass was measured.Specifically, a sample of material (about 0.1 g) was degassed undervacuum at 120° C. for 960 minutes, and the butane isotherm was measuredusing a 3Flex High Resolution High-throughput Surface CharacterizationAnalyzer. The adsorptive test gas used was butane. During the analysis,a temperature of 298′K was maintained with a circulating bath of awater/ethylene glycol mixture. Low pressure dose amounts were 0.5 cc ofbutane gas per gram of sample (cc/g) up to 0.000000100 P/Po, and 3.0cc/g up to 0.001 P/Po. An equilibration interval of 30 seconds was usedup to 0.001 P/Po, and an equilibration interval of 10 seconds was usedfor the rest of the isotherm. The data for the comparative example wasdivided by the carbon content (31.8%) to obtain the capacity of just thecarbon. The adsorbent materials tested by this procedure are listedbelow in Table 2:

TABLE 2 Adsorbent material properties Material BET Surface Area (m²/g)Carbon 1 1516 Carbon 4 1480 Carbon 5 2513 Carbon 6 1365

Carbons 4, 5, and 6 were used as further comparative examples. Carbon 4and Carbon 5 were commercially available active carbons marketed for useas canister carbons. These materials were received as extruded pelletsand ground into powder with a mortar and pestle before testing. Carbon 6was the activated carbon from an extruded honeycomb used in evaporativecanister scrubber applications. The scrubber was ground into a powderwith a mortar and pestle before testing. The test results werenormalized by the carbon content of the scrubber material, which wasmeasured to be 31.8% by LOI up to 1000° C.

Butane Isotherm Results

The results of the butane isotherm measurements for these samples(carbons 1, 4, 5, and 6; carbon 6 is referred to as “ComparativeExample” in FIGS. 6A-F) are provided in FIG. 6A. The data was plottedvs. the absolute pressure of butane in units of mm Hg. This data can becorrelated to evaporative emission applications by defining the absolutepartial pressure of butane at 760 mg Hg (i.e., atmospheric pressure)equal to a “butane percentage” of “100% butane” and plotting theadsorbed amount of butane vs. butane percentage, shown in FIG. 6B. Thedata was plotted up to a butane percentage of 50%, as this represents arelevant butane percentage for evaporative emission control applicationbecause the butane concentration typically used to measure the BWC ofevaporative emission control devices (e.g., ASTM D5528, USCAR02) is 50%butane. A plot of the same data normalized in terms of the amount ofbutane adsorbed by the material as a fraction of the total amount ofbutane adsorbed at 50% butane is provided as FIG. 6C.

The relative amounts of butane adsorbed by these materials at lowerbutane percentages are of more relevance to certain evaporative emissionapplications, such as a hydrocarbon adsorber (HCA) used to reduceevaporative emissions originating from the air intake system (AIS) of avehicle during a SHED test. Estimated vapor concentrations that atypical HCA would experience during a SHED test are on the order of ˜5%butane, depending on the size of the air cleaner housing. The vaporconcentration that a scrubber experiences during the diurnal portion ofa BETP test is on the order of 0.5% butane. Therefore, without wishingto be bound by theory, a material with an isotherm shape that isinitially comparatively steep at low butane percentages up to 5% butane,and flatter between butane percentages of 5% butane and 50% butane,would be expected to perform better in these applications.

FIG. 6D depicts the amount of butane adsorbed by these materials at 50%butane measured by the butane isotherm. These values were determined byreading the value for each material in Figure B at 50% butane.

FIGS. 6E and 6F provide the relative amounts that these materials adsorbat 5% and 0.5% butane as a fraction of the amount that material adsorbsat 50% butane. These values were defined as the Butane Affinity forthese materials at butane concentrations of 5% and 0.5%, respectively.The Butane Affinity for each material was determined by reading thevalue for each material at butane concentrations of 5% and 0.5% fromFIG. 6C. Specifically, the Butane Affinity was calculated by setting theabsolute partial pressure of butane at 760 mg Hg (i.e., atmosphericpressure) equal to a “Butane Percentage” of 100% and then plotting theadsorbed amount of butane vs. butane percentage as represented in FIG.6B. The data curve was then normalized by plotting the amount of butaneadsorbed as a fraction of the amount of butane adsorbed at a ButanePercentage of 50% as represented in FIG. 6C. The Butane Affinity at 0.5%and 5% butane was then determined from this plot by reading the fractionof butane adsorbed at 50% at these butane concentrations. In otherwords, the Butane Affinity of the material at 5% and 0.5% respectivelywas the percentage of the butane that the material adsorbed at butanepartial pressures of 38 mm Hg and 3.8 mmHg, respectively, compared tothe amount of butane that the material adsorbed at 380 mm Hg asdetermined by the butane isotherm measurement.

Based on the data in FIG. 6D alone, Carbon 1 would not be expected tohave particularly advantageous performance in AIS and scrubberapplications because it has butane adsorption capacities similar to orlower than the other carbons. However, the Butane Affinity at both 5%butane and 0.5% butane, as shown in FIGS. 6E and 6F, demonstrated thatthis material had an advantage over other materials used for evaporativeemission control. A Butane Affinity at 5% of >60% (exhibited by Carbon1; FIG. 6E) is unique and unexpected when compared to standardevaporative adsorbent materials, and is expected to result in improvedevaporative emission capture efficiency. A Butane Affinity at 0.5%of >35% (exhibited by Carbon 1; FIG. 6F) is unique and unexpected whencompared to standard evaporative adsorbent materials, and is expected toresult in improved evaporative emission capture efficiency. Accordingly,utilizing such materials in these applications would be expected toprovide better evaporative performance than standard adsorbents, or useless of such materials and still exhibit equivalent performance.

Example 6: Measurement of Butane Adsorption Capacity

A commercial carbon monolith (Comparative Example) and several coatedmonoliths (Examples 1-3), were tested in a butane absorption-desorptionsetup.

The 29×100 mm size cylindrical samples were placed inside a cylindricalsample cell oriented in the vertical direction. The sample cell was thenloaded with a 1:1 butane/N₂ test gas flow rate of 134 mL/min (10 g/hourof butane flow) for 45 minutes. The direction of flow was upward fromthe bottom of the sample cell to the top. The gas composition of theoutlet flow from the sample cell was monitored by an FID (FlameIonization Detector).

After the 45 minute butane adsorption step, the sample cell was purgedwith N₂ at 100 mL/min for 10 minutes in the same flow direction. Thesample was then desorbed with a 10 L/min flow of air in the oppositedirection (top to bottom) for 15 minutes. In the following step the gascomposition was switched to a mixture of 0.5% butane/N₂ at 134 ml/min(0.1 g butane per hour) and loading step was repeated. The breakthroughcurve was recorded using the FID described above and the signal wasplotted against the cumulative mass of butane flowing.

The relative effective butane adsorption capacity can be correlated tothe time it takes for butane breakthrough to occur through the sample.Butane breakthrough was defined as the time at which the outletconcentration of butane from the sample cell reached 25% of thesaturation concentration. In this test set-up, it was apparent (FIG. 7 )that only Example 1 (using carbon 1) provided comparable adsorptioncapacity to the commercial reference (Comparative Example). Theseresults demonstrated a dependence on the surface area, micropore volume,and shape of the butane isotherm.

Among the materials tested (Examples 1-3 and the Comparative Example),only Example 1 exhibited a breakthrough point that was comparable orsuperior to that of the Comparative Example. Without wishing to be boundby theory, this was believed to have been achieved through thecombination of high micropore volume at pore sizes of 0.3-1 nm and highmesopore volume at pore sizes 1-30 nm. The relevant parameters aresummarized in Table 3. The desired combination of high micropore volume,high mesopore volume, and high adsorption capacity at low partialpressure of butane was only achieved by the carbon in Example 1 (Carbon1). The resulting breakthrough point was the highest for this carbon.

TABLE 3 Parameters associated with good performance of adsorptivecarbon-coated substrates. Adsorbed Breakthrough Micropore Mesoporebutane point volume volume at 3 mm Hg (20% of feed 0.3-1 nm 1-30 nmbutane pressure concentration) Carbon [ml/g] [ml/g] [ml/g] [g butane]Carbon 1 0.291 0.70 74 0.44 Carbon 2 0.285 0.10 68 0.38 Carbon 3 0.1451.15 39 0.30

Example 7: BETP Test of Evaporative Emission Control Canister withScrubber Prepared According to Example 1

BETP Test on 1.9 L Canisters

Two 1.9 L automotive canisters were tested according to the CaliforniaBleed Emission Test Procedure (BETP). These canisters contained twoseparate carbon beds. Both beds of this canister were filled withIngevity BAX 1500 carbon. The first carbon bed was approximately twicethe volume of the second carbon bed. The canister also had an internalchamber for a scrubber. Prior to the test, a scrubber that had beenprepared according to Example 1 was installed in the scrubber chamber ofone of the canisters and the scrubber chamber of the other canister wasleft empty.

BETP Test Procedure:

The published procedure “USCAR Advanced Powertrain Technical LeadershipCouncil: Advanced Evaporative Technical Partnership; USCAR LEVIII/Tier 4BETP Recommended Procedure Based on Published Regulations” (May 23,2014) was employed. Gasoline fuel vapor (EPA test fuel) and dry nitrogen(1:1 fuel vapor/N₂ ratio) was loaded into each canister at a load rateof 40 g/hour until 2 g of fuel vapor breakthrough was detected, followedby a purge of dry air at 22.7 L/min for 300 bed volumes. This procedurewas repeated for a total of 10 load/purge cycles. The canister was thenloaded with butane (1:1 in nitrogen) to 2 g of breakthrough and allowedto soak for 1 hour. The canister was then purged at 22.7 L/min 40% RHair at 25° C. until the canister lost 76.8 g of mass, equivalent to 135bed volumes. The canister was then connected to a 14.5-gallon fuel tankthat had been filled 40% full with CARB Phase III fuel and soaked for 6hours at 65° F. The purge port of the canister was capped and the systemwas soaked for 12 hours at 65° F. The system was then cycled between 65°F. and 105° F. with a 12-hour ramp time for a total of two diurnalcycles (48 hours total). The canister outlet was open to an evaporativeemission measurement enclosure to monitor the evaporative emissions thatescaped from the canister. The highest hydrocarbon emission for each24-hour period was reported.

The highest day diurnal emissions were 275 mg for the canisters with noscrubber, but only 9 mg with the canister with the scrubber preparedaccording to Example 1. For both canisters, the highest day of emissionswas the second day. This result demonstrated that a scrubber preparedaccording to Example 1 can enable an automotive carbon canister to passthe <20 mg emission limit of the California Bleed Emission TestProcedure (BETP).

BETP Test on a 2.5 L Canister

A 2.5 L automotive canister was tested according to the California BleedEmission Test Procedure (BETP). This canister contained two separatecarbon beds. Both beds of this canister were filled with Ingevity BAX1500 carbon. The first carbon bed was approximately twice the volume ofthe second carbon bed. The canister did not have an internal chamber fora scrubber. To include a scrubber on this canister, a scrubber that hadbeen prepared according to Example 1 was placed in a separate housingand attached to the vent side port of the canister with a hose clamp andleak tested to ensure that it was sealed. The canister was testedaccording to the BETP test procedure as described above, with theexception that the canister was purged with 80 bed volumes of air afterthe butane load step. The highest day diurnal emission was 3 mg for thiscanister. The highest day of emission was the second day. This resultdemonstrated that a scrubber prepared according to Example 1 can enablean automotive carbon canister to pass the <20 mg emission limit of theCalifornia Bleed Emission Test Procedure (BETP).

What is claimed is:
 1. An evaporative emission control canister systemcomprising: an evaporative emission control canister comprising no morethan one canister adsorbent volume comprising a canister adsorbentmaterial having a total canister adsorbent material volume, and no morethan one bleed emission scrubber; wherein the bleed emission scrubbercomprises no more than one scrubber adsorbent volume, wherein thescrubber adsorbent volume comprises a scrubber adsorbent material andhas a g-total butane working capacity (BWC) of 0.1 grams to less than 2grams, wherein the g-total BWC is computed based on the total scrubberadsorbent volume and ASTM D5228 as of Jul. 16, 2018; wherein the bleedemission scrubber is in fluid communication with the evaporativeemission control canister; wherein the evaporative emission controlcanister system is configured to permit sequential contact of thecanister adsorbent volume and the scrubber adsorbent volume by fuelvapor; and wherein the evaporative emission control canister system hasa 2-Day Diurnal Breathing Loss (DBL) of less than about 20 mg under theCalifornia Bleed Emission Test Protocol (BETP) as of Mar. 22, 2012, whentested under the following test conditions: (i) the total canisteradsorbent material volume in the evaporative emission control canisteris 2.5 L and at a purge volume of 80 bed volumes; or (ii) the totalcanister adsorbent material volume in the evaporative emission controlcanister is 1.9 L and at a purge volume of 135 bed volumes.
 2. Theevaporative emission control canister system of claim 1, furthercomprising a fuel vapor purge tube for connecting the evaporativeemission control canister to an engine, a fuel vapor inlet conduit forventing a fuel tank to the evaporative emission control canister, and avent conduit for venting the evaporative emission control canister tothe atmosphere and for admission of purge air to the evaporativeemission control canister.
 3. The evaporative emission control canistersystem of claim 1, wherein the canister adsorbent material is selectedfrom the group consisting of activated carbon, carbon charcoal,zeolites, clays, porous polymers, porous alumina, porous silica,molecular sieves, kaolin, titania, ceria, and combinations thereof. 4.The evaporative emission control canister system of claim 3, wherein theactivated carbon is derived from a material including a member selectedfrom the group consisting of wood, wood dust, wood flour, cottonlinters, peat, coal, coconut, lignite, carbohydrates, petroleum pitch,petroleum coke, coal tar pitch, fruit pits, fruit stones, nut shells,nut pits, sawdust, palm, vegetables, synthetic polymer, natural polymer,lignocellulosic material, and combinations thereof.
 5. The evaporativeemission control canister system of claim 1, wherein the scrubberadsorbent material comprises a particulate carbon, wherein theparticulate carbon has a Brunauer Emmett Teller (BET) surface area of atleast about 1300 m²/g; and at least one of: i. a butane affinity ofgreater than 60% at 5% butane; ii. a butane affinity of greater than 35%at 0.5% butane; iii. a micropore volume greater than about 0.2 ml/g anda mesopore volume greater than about 0.5 ml/g.
 6. The evaporativeemission control canister system of claim 5, wherein the particulatecarbon has an n-butane adsorption capacity of at least about 40 ml/g atabout 3 mm Hg n-butane pressure.
 7. The evaporative emission controlcanister system of claim 5, wherein the particulate carbon has a BETsurface area of from about 1300 m²/g to about 2500 m²/g.
 8. Theevaporative emission control canister system of claim 5, wherein theparticulate carbon has a micropore volume of from about 0.20 ml/g toabout 0.35 ml/g.
 9. The evaporative emission control canister system ofclaim 5, wherein the particulate carbon has a mesopore volume of fromabout 0.5 ml/g to about 0.8 ml/g.
 10. The evaporative emission controlcanister system of claim 5, wherein the particulate carbon has a BETsurface area of about 1400 m²/gram, a micropore volume of about 0.3ml/g, and a mesopore volume of about 0.75 ml/g.
 11. The evaporativeemission control canister system of claim 5, wherein the bleed emissionscrubber comprises a substrate.
 12. The evaporative emission controlcanister system of claim 11, wherein the substrate is selected from thegroup consisting of foams, monolithic materials, non-wovens, wovens,sheets, papers, twisted spirals, ribbons, structured media of extrudedform, structured media of wound form structured media of folded form,structured media of pleated form, structured media of corrugated form,structured media of pored form, structured media of bonded form, andcombinations thereof.
 13. The evaporative emission control canistersystem of claim 11, wherein the substrate is molded, formed or extrudedwith a mixture comprising the scrubber adsorbent material.
 14. Theevaporative emission control canister system of claim 11, wherein thesubstrate comprises a coating, wherein the coating comprises thescrubber adsorbent material and a binder.
 15. The evaporative emissioncontrol canister system of claim 14, wherein the coating thickness isless than about 500 microns.
 16. The evaporative emission controlcanister system of claim 14, wherein the binder is present in an amountfrom about 10% to about 50% by weight relative to the particulatecarbon.
 17. The evaporative emission control canister system of claim14, wherein the binder is an organic polymer.
 18. The evaporativeemission control canister system of claim 1, wherein the scrubberadsorbent volume has an effective BWC of from about 0.5 grams/dl to lessthan 2 grams/dl.
 19. The evaporative emission control canister system ofclaim 1, wherein the evaporative emission control canister has acanister adsorbent volume of 3.5 L or less, 3.0 L or less, 2.5 L orless, or 2.0 L or less.
 20. The evaporative emission control canistersystem of claim 1, wherein the evaporative emission control canistersystem has a 2-Day Diurnal Breathing Loss (DBL) of less than about 10 mgunder the California Bleed Emission Test Protocol (BETP) as of Mar. 22,2012.